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Sample records for 3-deoxy-d-erythro-hexos-2-ulose bis thiosemicarbazone

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Binuclear ruthenium(III) bis(thiosemicarbazone) complexes: synthesis, spectral, electrochemical studies and catalytic oxidation of alcohol.

    PubMed

    Mohamed Subarkhan, M; Ramesh, R

    2015-03-05

    A new series of binuclear ruthenium(III) thiosemicarbazone complexes of general formula [(EPh3)2(X)2Ru-L-Ru(X)2(EPh3)2] (where E=P or As; X=Cl or Br; L=NS chelating bis(thiosemicarbazone ligands) has been synthesized and characterized by analytical and spectral (FT-IR, UV-Vis and EPR). IR spectra show that the thiosemicarbazones behave as monoanionic bidentate ligands coordinating through the azomethine nitrogen and thiolate sulphur. The electronic spectra of the complexes indicate that the presence of d-d and intense LMCT transitions in the visible region. The complexes are paramagnetic (low spin d(5)) in nature and all the complexes show rhombic distortion around the ruthenium ion with three different 'g' values (gx≠gy≠gz) at 77K. All the complexes are redox active and exhibit an irreversible metal centered redox processes (Ru(III)-Ru(III)/Ru(IV)-Ru(IV); Ru(III)-Ru(III)/Ru(II)-Ru(II)) within the potential range of 0.38-0.86V and -0.39 to -0.66 V respectively, versus Ag/AgCl. Further, the catalytic efficiency of one of the complexes [Ru2Cl2(AsPh3)4(L1)] (4) has been investigated in the case of oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N-methylmorpholine-N-oxide(NMO) as co-oxidant. The formation of high valent Ru(V)O species is proposed as catalytic intermediate for the catalytic cycle.

  3. Microwave gallium-68 radiochemistry for kinetically stable bis(thiosemicarbazone) complexes: structural investigations and cellular uptake under hypoxia.

    PubMed

    Alam, Israt S; Arrowsmith, Rory L; Cortezon-Tamarit, Fernando; Twyman, Frazer; Kociok-Köhn, Gabriele; Botchway, Stanley W; Dilworth, Jonathan R; Carroll, Laurence; Aboagye, Eric O; Pascu, Sofia I

    2016-01-07

    We report the microwave synthesis of several bis(thiosemicarbazones) and the rapid gallium-68 incorporation to give the corresponding metal complexes. These proved kinetically stable under 'cold' and 'hot' biological assays and were investigated using laser scanning confocal microscopy, flow cytometry and radioactive cell retention studies under normoxia and hypoxia. (68)Ga complex retention was found to be 34% higher in hypoxic cells than in normoxic cells over 30 min, further increasing to 53% at 120 min. Our data suggests that this class of gallium complexes show hypoxia selectivity suitable for imaging in living cells and in vivo tests by microPET in nude athymic mice showed that they are excreted within 1 h of their administration.

  4. Cu(II) Bis(thiosemicarbazone) Radiopharmaceutical Binding to Serum Albumin: Further Definition of Species-Dependence and Associated Substituent Effects

    PubMed Central

    Basken, Nathan E.; Green, Mark A.

    2009-01-01

    Introduction The Cu-PTSM (pyruvaldehyde bis(N4-methylthiosemicarbazonato)copper(II)) and Cu-ATSM (diacetyl bis(N4-methylthiosemicarbazonato)copper(II)) radiopharmaceuticals exhibit strong, species-dependent binding to the IIA site of human serum albumin (HSA), while the related Cu-ETS (ethylglyoxal bis(thiosemicarbazonato)copper(II)) radiopharmaceutical appears to only exhibit non-specific binding to human and animal serum albumins. Methods To further probe the structural basis for the species-dependence of this albumin binding interaction, protein binding of these three radiopharmaceuticals was examined in solutions of albumin and/or serum from a broader array of mammalian species (rat, sheep, donkey, rabbit, cow, pig, dog, baboon, mouse, cat, 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. PMID:19520290

  5. Partial conversion of thioamide into nitrile in a copper(II) complex of 2,6-diacetylpyridine bis(thiosemicarbazone), a drug prototype for Alzheimer's disease.

    PubMed

    Vieira, Rafael P; Thompson, John R; Beraldo, Heloisa; Storr, Tim

    2015-06-01

    This work reports the crystal structure of [(Z)-2-((E)-1-{6-[1-({[amino(sulfanidyl-κS)methylidene]amino}imino-κN)ethyl]pyridin-2-yl-κN}ethylidene)-1-cyanohydrazinido-κN(1)]copper(II), [Cu(C11H11N7S)], the first description of a copper(II) complex of 2,6-diacetylpyridine bis(thiosemicarbazone) showing partial conversion of a thioamide group to a nitrile group. The asymmetric ligand coordinates to the metal centre in an N,N',N'',S-tetradentate manner via the pyridine N atom, an imine N atom, the hydrazinide N atom and the sulfanidyl S atom, displaying a square-planar geometry. Ligand coordination results in two five-membered chelate rings and one six-membered chelate ring, and in crystal packing based on N-H···N hydrogen bonds of the cyanohydrazinide and hydrazinecarbothioamidate arms of the ligand. The correlation between the partial conversion upon metal complexation, H2S release and possible effects on the activity of bis(thiosemicarbazone)s as drug prototypes for Alzheimer's disease is also discussed.

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

    PubMed

    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.

  7. Evaluation of copper-labeled Cu(II) bis(thiosemicarbazone) complexes as blood flow tracers for positron emission tomography

    SciTech Connect

    Bott, A.J.

    1990-01-01

    Positron emmision tomography (PET) is an imaging technique not widely available for clinical diagnosis due to the costs of producing positron-emitting radiolabels. The development of radiotracers labeled with generator-produced positron emitters would facilitate the use of PET by eliminating the need for an in-house cyclotron. Copper-62 is a generator-produced positron emitter potentially useful for labeling PET radiopharmaceuticals. Copper-62 labeled Cu(II) pyruvaldehyde bis(N[sup 4]-methylthiosemicarbazone), Cu(PTSM), is a proposed PET perfusion tracer of the brain, heart, and kidneys. After IV injection in animals, copper-labeled Cu(PTSM) affords high initial uptake followed by prolonged retention of radiocopper in these organs. This retention is thought to be a result of reductive decomposition of the copper-labeled copper(II) complex by intracellular glutathione, GSH. To validate copper-62 labeled Cu(PTSM) as a myocardial and renal perfusion tracer, the regional radiocopper level afforded by intravenous copper-67 labeled Cu(PTSM) was compared to the absolute blood flow measured with labeled microspheres in normal dog kidneys and surgically infarcted myocardia. In the heart and randomly sectioned kidneys, an excellent correlation resulted. In kidneys dissected to separate anatomical regions, radiocopper levels increased montonically with increasing blood flows for individual dogs, but a linear correlation was observed when data from 12 animals was combined. Should the distribution of Cu(PTSM) vary with naturally occuring GSH fluctuations, the clinical utility of this radiotracer would be limited. Therefore, to validate further copper-62 labeled Cu(PTSM), the biodistribution of copper-67 labeled (PTSM) was determined in GSH-depleted rats. Relatively large GSH reductions in the experimental animals caused only slight changes in the distribution of Cu(PTSM). Another 23 copper-67 labeled compounds were tested.

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

    PubMed Central

    Parker, Erica N.; Song, Jiangli; Kumar, G. D. Kishore; Odutola, Samuel O.; Chavarria, Gustavo E.; Charlton-Sevcik, Amanda K.; Strecker, Tracy E.; Barnes, Ashleigh L.; Sudhan, Dhivya R.; Wittenborn, Thomas R.; Siemann, Dietmar W.; Horsman, Michael R.; Chaplin, David J.; Trawick, Mary Lynn; Pinney, Kevin G.

    2016-01-01

    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 studies on benzophenone thiosemicarbazone cathepsin inhibitors, a series of fourteen benzoylbenzophenone thiosemicarbazone analogues were designed, synthesized, and evaluated for their inhibitory activity against cathepsins L and B. Thiosemicarbazone inhibitors 3-benzoylbenzophenone thiosemicarbazone 1, 1,3-bis(4-fluorobenzoyl)benzene thiosemicarbazone 8, and 1,3-bis(2-fluorobenzoyl)-5-bromobenzene thiosemicarbazone 32 displayed the greatest potency against cathepsin L with low IC50 values of 9.9 nM, 14.4 nM, and 8.1 nM, respectively. The benzoylbenzophenone thiosemicarbazone analogues evaluated were 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 10 μM. Thiosemicarbazone analogue 8 significantly inhibited the invasive potential of PC-3ML prostate cancer cells by 92% at 5 μM. The most active cathepsin L inhibitors from this benzoylbenzophenone thiosemicarbazone series (1, 8, and 32) displayed low cytotoxicity toward normal primary cells [in this case human umbilical vein endothelial cells (HUVECs)]. In an initial in vivo study, 3-benzoylbenzophenone thiosemicarbazone (1) 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. Active members of this structurally diverse group of benzoylbenzophenone thiosemicarbazone cathepsin L inhibitors show promise as potential anti-metastatic, pre

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

    PubMed

    Parker, Erica N; Song, Jiangli; Kishore Kumar, G D; Odutola, Samuel O; Chavarria, Gustavo E; Charlton-Sevcik, Amanda K; Strecker, Tracy E; Barnes, Ashleigh L; Sudhan, Dhivya R; Wittenborn, Thomas R; Siemann, Dietmar W; Horsman, Michael R; Chaplin, David J; Trawick, Mary Lynn; Pinney, Kevin G

    2015-11-01

    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 studies on benzophenone thiosemicarbazone cathepsin inhibitors, a series of fourteen benzoylbenzophenone thiosemicarbazone analogues were designed, synthesized, and evaluated for their inhibitory activity against cathepsins L and B. Thiosemicarbazone inhibitors 3-benzoylbenzophenone thiosemicarbazone 1, 1,3-bis(4-fluorobenzoyl)benzene thiosemicarbazone 8, and 1,3-bis(2-fluorobenzoyl)-5-bromobenzene thiosemicarbazone 32 displayed the greatest potency against cathepsin L with low IC50 values of 9.9 nM, 14.4 nM, and 8.1 nM, respectively. The benzoylbenzophenone thiosemicarbazone analogues evaluated were 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 10 μM. Thiosemicarbazone analogue 8 significantly inhibited the invasive potential of PC-3ML prostate cancer cells by 92% at 5 μM. The most active cathepsin L inhibitors from this benzoylbenzophenone thiosemicarbazone series (1, 8, and 32) displayed low cytotoxicity toward normal primary cells [in this case human umbilical vein endothelial cells (HUVECs)]. In an initial in vivo study, 3-benzoylbenzophenone thiosemicarbazone (1) 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. Active members of this structurally diverse group of benzoylbenzophenone thiosemicarbazone cathepsin L inhibitors show promise as potential anti-metastatic, pre

  10. Microwave gallium-68 radiochemistry for kinetically stable bis(thiosemicarbazone) complexes: structural investigations and cellular uptake under hypoxia† †Electronic supplementary information (ESI) available. CCDC 1001632–1001634. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt02537k Click here for additional data file. Click here for additional data file.

    PubMed Central

    Alam, Israt S.; Arrowsmith, Rory L.; Cortezon-Tamarit, Fernando; Twyman, Frazer; Kociok-Köhn, Gabriele; Botchway, Stanley W.; Dilworth, Jonathan R.

    2016-01-01

    We report the microwave synthesis of several bis(thiosemicarbazones) and the rapid gallium-68 incorporation to give the corresponding metal complexes. These proved kinetically stable under ‘cold’ and ‘hot’ biological assays and were investigated using laser scanning confocal microscopy, flow cytometry and radioactive cell retention studies under normoxia and hypoxia. 68Ga complex retention was found to be 34% higher in hypoxic cells than in normoxic cells over 30 min, further increasing to 53% at 120 min. Our data suggests that this class of gallium complexes show hypoxia selectivity suitable for imaging in living cells and in vivo tests by microPET in nude athymic mice showed that they are excreted within 1 h of their administration. PMID:26583314

  11. Coordination of Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), Pd(II) and Pt(II) with 2,5-hexanedione bis(thiosemicarbazone), HBTS: Crystal structure of cis-[Pd(HBTS)]Cl2 and 1-(2,5-dimethyl-1H-pyrrol-yl)-thiourea

    NASA Astrophysics Data System (ADS)

    Jeragh, Bakir; El-Asmy, Ahmed A.

    2014-09-01

    Metal complexes of Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, Pd2+ or Pt2+ with 2,5-hexanedione bis(thiosemicarbazone), HBTS; have been prepared and spectroscopically investigated. The empirical formulae of the complexes were suggested based on the elemental analysis. Single crystal of Pd(II) has been solved to be cis-form of square-planar geometry by the X-ray crystallography. 1H and 13C NMR spectra have been recorded for HBTS, Zn(II), Cd(II), Hg(II), Pd(II) and Pt(II) complexes, in DMSO-d6, showing the mode of chelation. The ligand acts as a neutral or a binegative tetradentate (N2S2) or neutral bidentate on the basis of FT-IR. The magnetic moments and electronic spectra provide information about the geometry of the complexes which supported by calculating the ligand field parameters for the Co(II) and Fe(III) complexes. The Ni(II) complex has subnormal magnetic moment (0.71 BM) indicative of a mixed stereochemistry of square-planar and tetrahedral structure. [Cu(HBTS-2H)] measured 0.93 BM indicating high interaction between the copper centers. The ligand may be ordered at the top of the spectrochemical series which giving high ligand field splitting energy (10Dq = 17,900 cm-1 for Co2+ complex). The mass spectra of some complexes proved their stable chemical formulae while the TGA depicts the degradation steps and the final residue. In evaporating the mother liquor during the preparation of HBTS, new compound is obtained naming 1-(2,5-dimethyl-1H-pyrrol-yl)thiourea and its crystal was solved.

  12. Synthesis, Spectroscopic and Toxicity Studies of Titanocene Chelates of Isatin-3-Thiosemicarbazones

    PubMed Central

    Vatsa, Garima; Pandey, O. P.; Sengupta, S. K.

    2005-01-01

    The reactions of bis(cyclopentadienyl)titanium(IV) dichloride with a new class of thiosemicarbazone (LH2), derived by condensing isatin with different N(4)-substituted thiosemicarbazides, have been studied and products of type [Cp2Ti(L)] have been isolated. On the basis of various physico-chemical and spectral studies, five coordinate structures have been assigned to these derivatives. Toxicity studies of titanocene complexes at tbur different concentrations have been carried out against snail Lymnaea acuminata. The effect of most potent compounds on the activity of acetylcholinesterase enzyme, which inhibits the activity of enzyme, possibly by the formation of enzyme-inhibitor complex, was also studied. PMID:18365096

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

    PubMed Central

    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

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

    PubMed

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

    2013-01-01

    The palladium(II) bis-chelate complexes of the type [Pd(TSC(1-5))2] (6-10), with their corresponding ligands 4-phenyl-1-(acetone)-thiosemicarbazone, HTSC(1) (1), 4-phenyl-1-(2'-chloro-benzaldehyde)-thiosemicarbazone, HTSC(2) (2), 4-phenyl-1-(3'-hydroxy-benzaldehyde)-thiosemicarbazone, HTSC(3) (3), 4-phenyl-1-(2'-naphthaldehyde)-thiosemicarbazone, HTSC(4) (4), and 4-phenyl-1-(1'-nitro-2'-naphthaldehyde)-thiosemicarbazone, HTSC(5) (5), were synthesized and characterized by elemental analysis and spectroscopic techniques (IR and (1)H- and (13)C-NMR). The molecular structure of HTSC(3), HTSC(4), and [Pd(TSC(1))2] (6) have been determined by single crystal X-ray crystallography. Complex 6 shows a square planar geometry with two deprotonated ligands coordinated to Pd(II) 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(TSC(3))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.).

  15. Biological activity of complexes derived from pyridine-2-carbaldehyde thiosemicarbazone. Structure of.

    PubMed

    García-Tojal, J; García-Orad, A; Díaz, A A; Serra, J L; Urtiaga, M K; Arriortua, M I; Rojo, T

    2001-04-01

    Biological studies on [Fe(L)2](NO3).0.5H2O (1), [Fe(L)2][PF6] (2), [Co(L)2](NCS) (3), [Ni(HL)2]Cl2.3H2O (4) and Cu(L)(NO3) (5), where HL=C7H8N4S, pyridine-2-carbaldehyde thiosemicarbazone, have been carried out. The crystal structure of compound 3 has been solved. It consists of discrete monomeric cationic entities containing cobalt(III) ions in a distorted octahedral environment. The metal ion is bonded to one sulfur and two nitrogen atoms of each thiosemicarbazone molecule. The thiocyanate molecules act as counterions. The copper(II) and iron(III) complexes react with reduced glutathione and 2-mercaptoethanol. The reaction of compound 1 with the above thiols causes the reduction of the metal ion and bis(thiosemicarbazonato)iron(II) species are obtained. The redox activity, and in particular the reaction with cell thiols, seems to be related to the cytotoxicity of these complexes against Friend erithroleukemia cells and melanoma B16F10 cells.

  16. [Study of the effect of thiosemicarbazones against Toxoplasma gondii].

    PubMed

    Gomes, Marco Antônio G B; Carreira, Gabriela M; Souza, Daniela P V; Nogueira, Paulo Marcos R; de Melo, Edésio J T; Maria, Edmilson J

    2013-04-01

    Toxoplasmosis is a neglected disease, with an estimated occurrence of one-third of the population worldwide. Research in medicinal chemistry has for some years been pursuing the development of new drugs against toxoplasmosis, because current treatments cause serious side effects in the patient. The use of thiosemicarbazones as an alternative option for the treatment of various diseases has been published in recent years, due to their, among others, anticancer, antimalarial, antitrypanosomal, antibacterial, and antitoxoplasmosis activities, the latter being the subject of this study, which is based upon biological analyses and tests of the response of Toxoplasma gondii in the presence of thiosemicarbazones.

  17. Organometallic ruthenium complexes with thiosemicarbazone ligands: Synthesis, structure and cytotoxicity of [(η6-p-cymene)Ru(NS)Cl]+ (NS = 9-anthraldehyde thiosemicarbazones)

    PubMed Central

    Beckford, Floyd A.; Leblanc, Gabriel; Thessing, Jeffrey; Shaloski, Michael; Frost, Brian J.; Li, Liya; Seeram, Navindra P.

    2009-01-01

    A series of half-sandwich arene-ruthenium complexes of the type [(η6-p-cymene) Ru(thiosemicarbazone)Cl]+ have been synthesized and their biological activity investigated. The first structurally characterized arene-ruthenium half-sandwich complex with a thiosemicarbazone ligand is reported. PMID:20160909

  18. Isatin based thiosemicarbazone derivatives as potential bioactive agents: Anti-oxidant and molecular docking studies

    NASA Astrophysics Data System (ADS)

    Haribabu, J.; Subhashree, G. R.; Saranya, S.; Gomathi, K.; Karvembu, R.; Gayathri, D.

    2016-04-01

    A new series of isatin based thiosemicarbazones has been synthesized from benzylisatin and unsubstituted/substituted thiosemicarbazides (1-5). The synthesized compounds were characterized by elemental analyses, and UV-Visible, FT-IR, 1H &13C NMR and mass spectroscopic techniques. Three dimensional molecular structure of three compounds (1, 3 and 4) was determined by single crystal X-ray crystallography. Anti-oxidant activity of the thiosemicarbazone derivatives showed their excellent scavenging effect against free radicals. In addition, all the compounds showed good anti-haemolytic activity. In silico molecular docking studies were performed to screen the anti-inflammatory and anti-tuberculosis properties of thiosemicarbazone derivatives.

  19. Cytotoxic behavior and spectroscopic characterization of metal complexes of ethylacetoacetate bis(thiosemicarbazone) ligand

    NASA Astrophysics Data System (ADS)

    El-Tabl, Abdou Saad; El-wahed, Moshira Mohamed Abd; Rezk, Ahmed Mahmoud Salah Mahmoud

    2014-01-01

    Reaction of Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ion with 2,4-dihydrazino-thioamido-1-ethoxybutane led to the formation of mono and binuclear complexes. These complexes have been characterized by elemental analyses, IR, UV-Vis spectra, magnetic moments, molar conductances, 1H NMR and mass spectra (ligand and its Zn(II) complex), thermal analyses (DTA and TGA) and ESR measurements. The IR data suggest the involvement of sulfur and azomethane nitrogen atoms in coordination to the central metal ion .The Molar conductances of the complexes in DMF are commensurate with their non-ionic character. The ESR spectra of Cu(II) complexes show axial type symmetry (d(x2-y2)) ground state with covalent bond character. On the basis of spectral studies, octahedral or tetrahedral geometry has been assigned to the metal complexes. Complexes have been tested invitro against tumor cells and number of microorganisms in order to assess their antitumor and antimicrobial properties.

  20. Spectral studies of copper(II) complexes of 6-(3-thienyl) pyridine-2-thiosemicarbazone

    SciTech Connect

    Mahjoub, Omima Abdalla; Farina, Yang

    2014-09-03

    Two novel copper(II) complexes [Cu(HL)Cl]Cl.H{sub 2}O (1) and [Cu(L)NO{sub 3}]Ðœ‡H{sub 2}O (2) of the three NNS donor thiosemicarbazone ligand 6-(3-thienyl) pyridine-2-thiosemicarbazone have been synthesized. The ligand and its copper(II) complexes were characterized by elemental analysis (C, H, N, and S), FT-IR, UV-visible, magnetic susceptibility and molar conductance. The thiosemicarbazone is present either as the thione form in complex 1 or as thiol form in complex 2 and is coordinated to copper(II) atom via the pyridine nitrogen atom, the azomethine nitrogen atom and the sulfur atom. The physicochemical and spectral data suggest square planar geometry for copper(II) atoms.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Effect of the Metal Ion on the Enantioselectivity and Linkage Isomerization of Thiosemicarbazone Helicates.

    PubMed

    Romero, María J; Suárez, Vanesa; Fernández-Fariña, Sandra; Maneiro, Marcelino; Martínez-Núñez, Emilio; Zaragoza, Guillermo; González-Noya, Ana M; Pedrido, Rosa

    2017-04-06

    The effect of the metal ion and ligand design on the enantioselectivity and linkage isomerization of neutral cobalt and zinc bisthiosemicarbazone metallohelicates has been investigated in this work. The electrochemical synthesis has afforded the enantioselective formation of chirally pure cobalt helicates, and the ΛΛ isomer of a single enantiomer has been crystallized as only product for the cobalt methyl-substituted thiosemicarbazone helicate. Interestingly linkage isomers have been formed from zinc ethyl-substituted thiosemicarbazone helicate enantiomers for the first time. The co-existence of these isomers has been evaluated from the point of view of both experimental results and computational calculations.

  3. A novel series of thiosemicarbazone drugs: From synthesis to structure

    NASA Astrophysics Data System (ADS)

    Ebrahimi, Hossein Pasha; Hadi, Jabbar S.; Alsalim, Tahseen A.; Ghali, Thaer S.; Bolandnazar, Zeinab

    2015-02-01

    A new series of thiosemicarbazones (TSCs) and their 1,3,4-thiadiazolines (TDZs) containing acetamide group have been synthesized from thiosemicarbazide compounds by the reaction of TSCs with cyclic ketones as well as aromatic aldehydes. The structures of newly synthesized 1,3,4-thiadiazole derivatives obtained by heterocyclization of the TSCs with acetic anhydride were experimentally characterized by spectral methods using IR, 1H NMR, 13C NMR and mass spectroscopic methods. Furthermore, the structural, thermodynamic, and electronic properties of the studied compounds were also studied theoretically by performing Density Functional Theory (DFT) to access reliable results to the experimental values. The molecular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) and Mulliken atomic charges of the studied compounds have been calculated at the B3LYP method and standard 6-31+G(d,p) basis set starting from optimized geometry. The theoretical 13C chemical shift results were also calculated using the gauge independent atomic orbital (GIAO) approach and their respective linear correlations were obtained.

  4. Calcium release induced by 2-pyridinecarboxaldehyde thiosemicarbazone and its copper complex contributes to tumor cell death.

    PubMed

    Fu, Yun; Liu, Youxun; Wang, Jiangang; Li, Cuiping; Zhou, Sufeng; Yang, Yun; Zhou, Pingxin; Lu, Chengbiao; Li, Changzheng

    2017-03-01

    Thiosemicarbazones display significant antitumor activity and their copper complexes also exhibit enhanced biological activities in most situations, but the underlying mechanism is poorly understood. Therefore, investigation of the mechanism involved in the change upon chelation is required to extend our understanding of the effects of thiosemicarbazones. In the present study, the inhibitory effect of 2-pyridinecarboxaldehyde thiosemicarbazone (PCT) and its copper complex (PCT-Cu) on cell proliferation was investigated. The copper chelate exhibited a 3- to 10-fold increase in antitumor activity (with an IC50 <5 µM). The results showed that both PCT and PCT-Cu induced reactive oxygen species (ROS) generation in vitro and in vivo, caused cellular DNA fragmentation, depolarization of the mitochondrial membrane and cell cycle arrest. Western blotting showed that both PCT and PCT-Cu induced apoptosis. Upregulation of GRP78 in HepG2 cells following treatment with the agents indicated that endoplasmic reticulum (ER) stress occurred. Furthermore calcium release was revealed in this study, suggesting that PCT and PCT-Cu disturbed calcium homeostasis. It was noted that PCT-Cu sensitized thapsigargin‑stimulated calcium release from the ER, which was correlated with the ROS level they induced, implying that the antitumor activity of PCT and PCT-Cu partly stemmed from calcium mobilization, a situation that was reported in few studies. Our findings may significantly contribute to the understanding of the anti‑proliferative effect of the derivatives of thiosemicarbazones along with their antitumor mechanism.

  5. Inhibition of RNA-dependent DNA polymerase of Rous sarcoma virus by thiosemicarbazones and several cations.

    PubMed

    Levinson, W; Faras, A; Woodson, B; Jackson, J; Bishop, J M

    1973-01-01

    The RNA-dependent DNA polymerase of Rous sarcoma virus is inhibited by N-methyl isatin beta-thiosemicarbazone and by thiosemicarbazide, but not by semicarbazide. These inhibitors also inactivate, upon contact with the virion, the transforming ability of Rous sarcoma virus. Sulfhydryl donors, such as 2-mercapto-ethanol, can prevent these effects. The RNA-directed activity of the purified polymerase is inhibited to a greater degree than is the DNA-directed activity. Two cations, Cu(++) and Hg(++), can inhibit RNA-dependent DNA polymerase and inactivate the transforming ability of the virus. Synergism between N-methyl isatin beta-thiosemicarbazone and Cu(++) occurs, since treatment of the virus with a low dose of either N-methyl isatin beta-thiosemicarbazone or Cu(++) has little effect; however, when the two compounds are mixed together, significant inactivation occurs. This observation supports the hypothesis that the antiviral action of thiosemicarbazones is a function of their ability to act as a ligand for metallic ions. Several cations (Ag(+), Co(++), Zn(++), Cd(++), and Ni(++)) significantly inactivate the RNA-dependent DNA polymerase, but have little effect on the transforming ability. In view of this result, the conclusion that the enzyme activity is required for transformation remains open to question.

  6. Thiosemicarbazone modification of 3-acetyl coumarin inhibits Aβ peptide aggregation and protect against Aβ-induced cytotoxicity.

    PubMed

    Ranade, Dnyanesh S; Bapat, Archika M; Ramteke, Shefali N; Joshi, Bimba N; Roussel, Pascal; Tomas, Alain; Deschamps, Patrick; Kulkarni, Prasad P

    2016-10-04

    Aggregation of amyloid β peptide (Aβ) is an important event in the progression of Alzheimer's disease. Therefore, among the available therapeutic approaches to fight with disease, inhibition of Aβ aggregation is widely studied and one of the promising approach for the development of treatments for Alzheimer's disease. Thiosemicarbazone compounds are known for their variety of biological activities. However, the potential of thiosemicarbazone compounds towards inhibition of Aβ peptide aggregation and the subsequent toxicity is little explored. Herein, we report synthesis and x-ray crystal structure of novel compound 3-acetyl coumarin thiosemicarbazone and its efficacy toward inhibition of Aβ(1-42) peptide aggregation. Our results indicate that 3-acetyl coumarin thiosemicarbazone inhibits Aβ(1-42) peptide aggregation up to 80% compared to the parent 3-acetyl coumarin which inhibits 52%. Further, 3-acetyl coumarin thiosemicarbazone provides neuroprotection against Aβ-induced cytotoxicity in SH-SY5Y cell line. These findings indicate that thiosemicarbazone modification renders 3-acetyl coumarin neuroprotective properties.

  7. Cytotoxic and antimicrobial effects of indium(iii) complexes with 2-acetylpyridine-derived thiosemicarbazones.

    PubMed

    Oliveira, Alexandre A; Perdigão, Gabriele M C; Rodrigues, Luana E; da Silva, Jeferson G; Souza-Fagundes, Elaine M; Takahashi, Jacqueline A; Rocha, Willian R; Beraldo, Heloisa

    2017-01-17

    Complexes [In(2Ac4oClPh)Cl2(MeOH)] (1), [In(2Ac4pFPh)Cl2(MeOH)] (2), [In(2Ac4pClPh)Cl2(MeOH)] (3) and [In(2Ac4pIPh)Cl2(MeOH)] (4) were obtained with N(4)-ortho-chlorophenyl-2-acetylpyridine thiosemicarbazone (H2Ac4oClPh), N(4)-para-fluorophenyl-2-acetylpyridine thiosemicarbazone (H2Ac4pFPh), N(4)-para-chlorophenyl-2-acetylpyridine thiosemicarbazone (H2Ac4pClPh) and N(4)-para-iodophenyl-2-acetylpyridine thiosemicarbazone (H2Ac4pIPh). Theoretical studies suggested that the coordinated methanol molecule can be easily replaced by DMSO used in the preparation of stock solutions, with the formation of [In(L)Cl2(DMSO)] (HL = thiosemicarbazonate ligand), and that the replacement of DMSO by water is unfavorable. However, for all complexes the displacement of one or two chloride ligands by water in aqueous solution is extremely favorable. The cytotoxic activity of the compounds was evaluated against HL-60, Jurkat and THP-1 leukemia and against MDA-MB-231 and HCT-116 solid tumor cell lines, as well as against Vero non-malignant cells. The cytotoxicity and selectivity indexes (SI) increased in several cases for the indium(iii) complexes in comparison with the free thiosemicarbazones. The antimicrobial activity of the compounds was investigated against Candida albicans, Candida dubliniensis, Candida lusitaniae and Candida parapsilosis. In many cases complexation resulted in a substantial increase of the antifungal activity. Complexes (1-4) were revealed to be very active against C. lusitaniae and C. dubliniensis. Structure-activity relationship (SAR) studies were carried out to identify the physico-chemical properties that might be involved in the antifungal action, as well as in the cytotoxic effect of the compounds against HL-60 cells. In both cases, correlations between the bioactivity and physico-chemical properties did not appreciably change when the chloride ligands in [In(L)Cl2(DMSO)] were replaced by water molecules, suggesting [In(L)Cl(H2O)(DMSO)](+) or [In(L)(H2O)2

  8. Synthesis and Antiproliferative Activity of Steroidal Thiosemicarbazone Platinum (Pt(II)) Complexes

    PubMed Central

    Huang, Yanmin; Kong, Erbin; Gan, Chunfang; Liu, Zhiping; Lin, Qifu; Cui, Jianguo

    2015-01-01

    Steroidal compounds exhibit particular physiological activities. In this paper, some steroidal thiosemicarbazones platinum (Pt(II)) complexes were synthesized by the condensation of steroidal ketones with thiosemicarbazide using estrone, chenodeoxycholic acid, and 7-deoxycholic acid as starting materials and complexation of steroidal thiosesemicarbazones with Pt(II). The complexes were characterized by IR, NMR, and MS, and their antiproliferative activities were evaluated. The results showed that some steroidal thiosemicarbazones platinum (Pt(II)) complexes displayed moderate cytotoxicity to HeLa and Bel-7404 cells. Thereinto, complex 6 showed an excellent inhibited selectivity to HeLa cells with an IC50 value of 9.2 μM and SI value of 21.7. At the same time, all compounds were almost inactive to HEK293T (normal kidney epithelial cells). The information obtained from the studies may be useful for the design of novel chemotherapeutic drugs. PMID:26635511

  9. Synthesis, physicochemical properties, and in vitro antibacterial screening of palladium(II) complexes derived from thiosemicarbazone.

    PubMed

    Azam, Mohammad; Warad, Ismail; Al-Resayes, Saud I; Siddiqui, M Rafiq; Oves, M

    2013-06-01

    A new series of PdII complexes derived from thiosemicarbazone has been synthesized. The synthesized PdII complexes have been characterized on the basis of elemental analyses, FT-IR, ¹H- and ¹³C-NMR, UV/VIS, and thermal studies. A square-planar geometry has been assigned around PdII ions on the basis of results obtained from UV/VIS studies. The thiosemicarbazone ligand and its PdII complexes have been screened against Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria in vitro as growth-inhibiting agents, and the results revealed significant antibacterial activities.

  10. In vitro antiparasitic activity of new thiosemicarbazones in strains of Trypanosoma cruzi.

    PubMed

    Moreno-Rodríguez, Adriana; Salazar-Schettino, Paz María; Bautista, Juan Luis; Hernández-Luis, Francisco; Torrens, Hugo; Guevara-Gómez, Yolanda; Pina-Canseco, Socorro; Torres, Martha Bucio; Cabrera-Bravo, Margarita; Martinez, Cesar Mendoza; Pérez-Campos, Eduardo

    2014-11-24

    In this study thiosemicarbazones derivatives of 5-[(trifluoromethyl)phenylthio]-2-furaldehyde were synthesized and evaluated in terms of their efficiency in challenging the growth of epimastigote forms of Trypanosoma cruzi, the etiological agent of Chagas' disease. A number of compounds were synthesized from 5-bromo-2-furfuraldehyde using nucleophilic aromatic substitution, with a series of trifluoromethyl thiolates, followed by condensation reactions with thiosemicarbazide. Their molecular structures were determined by (1)H, (13)C and (19)F NMR, MS and IR spectroscopy. When tested with T. cruzi, they showed a stronger reaction, similar to nifurtimox and benznidazole, with the 5-[nitro-4-(trifluoromethyl)phenyltio]-2-furaldehyde thiosemicarbazone (compound 4) showing the highest antiparasitic activity. This improved activity may be explained due to the nitro group present in the molecule, which potentiates its activity. The thiosemicarbazone derivatives in this study showed no apoptosis in platelets or monocytes, nor did they induce platelet activation. The trypanocidal activity of these substances represents a good starting point for a medicinal chemistry program aimed at therapy for Chagas' disease.

  11. Organotin(IV) complexes of 2-pyridineformamide-derived thiosemicarbazones: antimicrobial and cytotoxic effects.

    PubMed

    Mendes, Isolda C; Moreira, Juliana P; Ardisson, José D; Santos, Raquel Gouvea Dos; da Silva, Paulo Roberto O; Garcia, Isabel; Castiñeiras, Alfonso; Beraldo, Heloisa

    2008-07-01

    Reaction of n-butyltin trichloride [(n-Bu)SnCl(3)] with 2-pyridineformamide thiosemicarbazone (H2Am4DH) and its N(4)-methyl (H2Am4Me) and N(4)-ethyl (H2Am4Et) derivatives gave [(n-Bu)Sn(2Am4DH)Cl(2)] (1), [(n-Bu)Sn(2Am4Me)Cl(2)] (2), and [(n-Bu)Sn(2Am4Et)Cl(2)] (3). Thiosemicarbazones as well as their tin complexes are active as antimicrobials against the growth of Candida albicans and Salmonella typhimurium and were highly active against malignant glioblastoma. The cytotoxic activity of complexes 1-3 is similar. Among the studied compounds [(n-Bu)Sn(2Am4DH)Cl(2)] (1) was the most active as antiproliferative (cytostatic) agent. Thiosemicarbazones and their tin(IV) complexes proved to be more potent as cytotoxic agents than cisplatin. All the compounds were able to induce apoptosis.

  12. Complexes of 2-acetyl-gamma-butyrolactone and 2-furancarbaldehyde thiosemicarbazones: antibacterial and antifungal activity.

    PubMed

    Rodríguez-Argüelles, María C; Tourón-Touceda, Patricia; Cao, Roberto; García-Deibe, Ana M; Pelagatti, Paolo; Pelizzi, Corrado; Zani, Franca

    2009-01-01

    Cobalt, nickel, copper and zinc coordination compounds of two thiosemicarbazones with general composition ML(2) (L: monodeprotonated ligand corresponding to 2-acetyl-gamma-butyrolactone thiosemicarbazone, HL(1), and 2-furancarbaldehyde thiosemicarbazone, HL(2)) and also complexes with general composition MCl(2)(HL(2)) were synthesized (except [NiCl(2)(HL(2))] and [Co(L(2))(2)]). The interaction of CuCl(2) with HL(2) gave [CuCl(HL(2))], a copper(I) complex. The ligands and metal complexes were characterized by IR, (1)H and (13)C NMR spectroscopy, and magnetic susceptibility measurements. The crystal structure of [Ni(L(2))(2)]x 2dmso was determined and a trans-square planar coordination of the two kappa(2)-N,S chelate rings forming polymeric strips through H-bonds with dmso was observed. Actually, in all the reported complexes both ligands behaved as kappa(2)-N,S chelates, except in the case of [Co(L(1))(2)] in which HL(1) is tridentate kappa(3)-N,S,O. The antimicrobial properties of all compounds were studied using a wide spectrum of bacterial and fungal strains. The copper complexes of HL(2) were the most active against all strains, including dermatophytes and phytopathogenic fungi. Most of the studied compounds, especially [Cu(L(1))(2)], presented good activity against Haemophilus influenzae, a very harmful bacterium to humans.

  13. Synthesis, characterization and binding affinities of rhenium(I) thiosemicarbazone complexes for the estrogen receptor (α/β).

    PubMed

    Núñez-Montenegro, Ara; Carballo, Rosa; Vázquez-López, Ezequiel M

    2014-11-01

    The binding affinities towards estrogen receptors (ERs) α and β of a set of thiosemicarbazone ligands (HL(n)) and their rhenium(I) carbonyl complexes [ReX(HL(n))(CO)3] (X=Cl, Br) were determined by a competitive standard radiometric assay with [(3)H]-estradiol. The ability of the coordinated thiosemicarbazone ligands to undergo deprotonation and the lability of the ReX bond were used as a synthetic strategy to obtain [Re(hpy)(L(n))(CO)3] (hpy=3- or 4-hydroxypyridine). The inclusion of the additional hpy ligand endows the new thiosemicarbazonate complexes with an improved affinity towards the estrogen receptors and, consequently, the values of the inhibition constant (Ki) could be determined for some of them. In general, the values of Ki for both ER subtypes suggest an appreciable selectivity towards ERα.

  14. Strong effect of copper(II) coordination on antiproliferative activity of thiosemicarbazone-piperazine and thiosemicarbazone-morpholine hybrids.

    PubMed

    Bacher, Felix; Dömötör, Orsolya; Chugunova, Anastasia; Nagy, Nóra V; Filipović, Lana; Radulović, Siniša; Enyedy, Éva A; Arion, Vladimir B

    2015-05-21

    In this study, 2-formylpyridine thiosemicarbazones and three different heterocyclic pharmacophores were combined to prepare thiosemicarbazone–piperazine mPip-FTSC (HL1) and mPip-dm-FTSC (HL2), thiosemicarbazone–morpholine Morph-FTSC (HL3) and Morph-dm-FTSC (HL4), thiosemicarbazone–methylpyrrole-2-carboxylate hybrids mPyrr-FTSC (HL5) and mPyrr-dm-FTSC (HL6) as well as their copper(II) complexes [CuCl(mPipH-FTSC-H)]Cl (1 + H)Cl, [CuCl(mPipH-dm-FTSC-H)]Cl (2 + H)Cl, [CuCl(Morph-FTSC-H)] (3), [CuCl(Morph-dm-FTSC-H)] (4), [CuCl(mPyrr-FTSC-H)(H2O)] (5) and [CuCl(mPyrr-dm-FTSC-H)(H2O)] (6). The substances were characterized by elemental analysis, one- and two-dimensional NMR spectroscopy (HL1–HL6), ESI mass spectrometry, IR and UV–vis spectroscopy and single crystal X-ray diffraction (1–5). All compounds were prepared in an effort to generate potential antitumor agents with an improved therapeutic index. In addition, the effect of structural alterations with organic hybrids on aqueous solubility and copper(II) coordination ability was investigated. Complexation of ligands HL2 and HL4 with copper(II) was studied in aqueous solution by pH-potentiometry, UV–vis spectrophotometry and EPR spectroscopy. Proton dissociation processes of HL2 and HL4 were also characterized in detail and microscopic constants for the Z/E isomers were determined. While the hybrids HL5, HL6 and their copper(II) complexes 5 and 6 proved to be insoluble in aqueous solution, precluding antiproliferative activity studies, the thiosemicarbazone–piperazine and thiosemicarbazone–morpholine hybrids HL1–HL4, as well as copper(II) complexes 1–4 were soluble in water enabling cytotoxicity assays. Interestingly, the metal-free hybrids showed very low or even a lack of cytotoxicity (IC50 values > 300 μM) in two human cancer cell lines HeLa (cervical carcinoma) and A549 (alveolar basal adenocarcinoma), whereas their copper(II) complexes were cytotoxic showing IC50 values from 25.5 to 65.1

  15. Structure-activity relationships for metal-labeled blood flow tracers: comparison of keto aldehyde bis(thiosemicarbazonato)copper(II) derivatives.

    PubMed

    John, E K; Green, M A

    1990-06-01

    Radiocopper-labeled pyruvaldehyde bis(N4-methylthiosemicarbazonato)copper(II), Cu[PTSM], is under investigation as a radiopharmaceutical for evaluation of regional blood flow in the brain, heart, and kidneys because it affords relatively high levels of radioactivity in these organs upon intravenous injection, followed by prolonged tissue retention of the radiolabel. To probe and differentiate the physicochemical properties that are critical for blood-brain barrier (BBB) penetration and tissue retention in complexes of this type, 17 67Cu-labeled copper(II) bis(thiosemicarbazone) derivatives of Cu[PTSM] have been prepared and characterized, focusing on the bis(thiosemicarbazone), bis(N4-methylthiosemicarbazone), bis(N4-dimethylthiosemicarbazone), and bis(N4-ethylthiosemicarbazone) derivatives of several alkylglyoxals (R(1) = Me, Et, n-Pr, i-Pr, n-Bu, or Me(EtO)CH) and phenylglyoxal. The compounds studied varied in lipophilicity from log P = 0.75 to log P = 3.5 (where P is the octanol/water partition coefficient). In rat biodistribution studies the N4-methylthiosemicarbazone (R(1)TSM) and N4-dimethylthiosemicarbazone (R(1)TSM2) complexes always show comparable cerebral uptake at 1 min postinjection (iv) for any given R(1) group, while the thiosemicarbazone (R(1)TS) complex always penetrates the BBB less efficiently. Comparison of the various Cu[R(1)TS] derivatives shows that their brain uptake does tend to increase with increasing lipophilicity over the range 0.75 less than log P less than 2.4, although it never reaches that of the N4-alkylated derivatives. The Cu[R(1)TS] and Cu[R(1)TSM] complexes are found to exhibit prolonged cerebral retention of activity, consistent with their known susceptibility to reductive decomposition by intracellular sulfhydryl groups, while the more inert Cu[R(1)TSM2] complexes clear from the brain relatively rapidly. Tracer clearance kinetics in the heart and kidney are similar to those observed for the brain with each of the tracers

  16. Novel heterocyclic thiosemicarbazones derivatives as colorimetric and "turn on" fluorescent sensors for fluoride anion sensing employing hydrogen bonding.

    PubMed

    Ashok Kumar, S L; Saravana Kumar, M; Sreeja, P B; Sreekanth, A

    2013-09-01

    Two novel heterocyclic thiosemicarbazone derivatives have been synthesized, and characterized, by means of spectroscopic and single crystal X-ray diffraction methods. Their chromophoric-fluorogenic response towards anions in competing solvent dimethyl sulfoxide (DMSO) was studied. The receptor shows selective recognition towards fluoride anion. The binding affinity of the receptors with fluoride anion was calculated using UV-visible and fluorescence spectroscopic techniques.

  17. Coordination to gallium(III) strongly enhances the potency of 2-pyridineformamide thiosemicarbazones against Cryptococcus opportunistic fungi.

    PubMed

    Bastos, Thaíssa de Oliveira; Soares, Betânia Maria; Cisalpino, Patrícia Silva; Mendes, Isolda Castro; dos Santos, Raquel Gouvea; Beraldo, Heloisa

    2010-09-20

    A family of 2-pyridineformamide-derived thiosemicarbazones and their gallium(III) complexes were tested against several isolates of pathogenic Cryptococcus strains. On complexation the antifungal activity significantly increases, suggesting coordination to gallium(III) to be an interesting strategy of antifungal dose reduction.

  18. Lanthanum(III) and praseodymium(III) complexes with isatin thiosemicarbazones.

    PubMed

    Rai, Anita; Sengupta, Soumitra K; Pandey, Om P

    2005-09-01

    Ten new lanthanum(III) and praseodymium(III) complexes of the general formula Na[La(L)2H2O] (Ln=La(III) or Pr(III); LH2=thiosemicarbazones) derived from the condensation of isatin with 4-phenyl thiosemicarbazide, 4-(4-chlorophenyl) thiosemicarbazide, 4-(2-nitrophenyl) thiosemicarbazide, 4-(2-bromophenyl) thiosemicarbazide and 4-(2-methylphenyl) thiosemicarbazide, have been synthesized in methanol in presence of sodium hydroxide. The XRD spectra of the complexes were monitored to verify complex formation. The complexes have also been characterized by elemental analysis, molar conductance, electronic absorption and fluorescence, infrared, far infrared, 1H and 13C NMR spectral studies. Thermal studies of these complexes have been carried out in the temperature range 25-800 degrees C using TG, DTG and DTA techniques. All these complexes decompose gradually with the formation of Ln2O3 as the end product. The Judd-ofelt intensity parameter, oscillator strength, transition probability, stimulated emission cross section for different transitions of Pr3+ for 4-phenyl thiosemicarbazones have been calculated.

  19. Vanadium(IV/V) complexes of Triapine and related thiosemicarbazones: Synthesis, solution equilibrium and bioactivity.

    PubMed

    Kowol, Christian R; Nagy, Nóra V; Jakusch, Tamás; Roller, Alexander; Heffeter, Petra; Keppler, Bernhard K; Enyedy, Éva A

    2015-11-01

    The stoichiometry and thermodynamic stability of vanadium(IV/V) complexes of Triapine and two related α(N)-heterocyclic thiosemicarbazones (TSCs) with potential antitumor activity have been determined by pH-potentiometry, EPR and (51)V NMR spectroscopy in 30% (w/w) dimethyl sulfoxide/water solvent mixtures. In all cases, mono-ligand complexes in different protonation states were identified. Dimethylation of the terminal amino group resulted in the formation of vanadium(IV/V) complexes with considerably higher stability. Three of the most stable complexes were also synthesized in solid state and comprehensively characterized. The biological evaluation of the synthesized vanadium complexes in comparison to the metal-free ligands in different human cancer cell lines revealed only minimal influence of the metal ion. Thus, in addition the coordination ability of salicylaldehyde thiosemicarbazone (STSC) to vanadium(IV/V) ions was investigated. The exchange of the pyridine nitrogen of the α(N)-heterocyclic TSCs to a phenolate oxygen in STSC significantly increased the stability of the complexes in solution. Finally, this also resulted in increased cytotoxicity activity of a vanadium(V) complex of STSC compared to the metal-free ligand.

  20. Cytotoxic gallium complexes containing thiosemicarbazones derived from 9-anthraldehyde: Molecular docking with biomolecules

    NASA Astrophysics Data System (ADS)

    Beckford, Floyd A.; Brock, Alyssa; Gonzalez-Sarrías, Antonio; Seeram, Navindra P.

    2016-10-01

    We have synthesized a trio of gallium complexes bearing 9-anthraldehyde thiosemicarbazones. The complexes were assessed for their anticancer activity and their biophysical reactivity was also investigated. The three complexes displayed good cytotoxic profiles against two human colon cancer cell lines, HCT-116 and Caco-2. The IC50 ranged from 4.7 to 44.1 μM with the complex having an unsubstituted amino group on the thiosemicarbazone being the most active. This particular complex also showed a high therapeutic index. All three complexes bind strongly to DNA via intercalation with binding constants ranging from 7.46 × 104 M-1 to 3.25 × 105 M-1. The strength of the binding cannot be directly related to the level of anticancer activity. The complexes also bind strongly to human serum albumin with binding constants on the order of 104-105 M-1 as well. The complexes act as chemical nucleases as evidenced by their ability to cleave pBR322 plasmid DNA. The binding constants along with the cleavage results may suggest that the extent of DNA interaction is not directly correlated with anticancer activity. The results of docking studies with DNA, ribonucleotide reductase and human serum albumin, however showed that the complex with the best biological activity had the largest binding constant to DNA.

  1. New organoruthenium complexes with bioactive thiosemicarbazones as co-ligands: potential anti-trypanosomal agents†

    PubMed Central

    Demoro, Bruno; Sarniguet, Cynthia; Sánchez-Delgado, Roberto; Rossi, Miriam; Liebowitz, Daniel; Caruso, Francesco; Olea-Azar, Claudio; Moreno, Virtudes; Medeiros, Andrea; Comini, Marcelo A.; Otero, Lucía; Gambino, Dinorah

    2012-01-01

    In the search for new therapeutic tools against neglected diseases produced by trypanosomatid parasites, and particularly against African Trypanosomiasis, whose etiological agent is Trypanosoma brucei, organoruthenium compounds with bioactive nitrofuran containing thiosemicarbazones (L) as co-ligands were obtained. Four ruthenium(ii) complexes with the formula [Ru2(p-cymene)2(L)2]X2, where X = Cl or PF6, were synthesized and the crystal structures of two of them were solved by X-ray diffraction methods. Two of the complexes show significant in vitro growth inhibition activity against Trypanosoma brucei brucei and are highly selective towards trypanosomal cells with respect to mammalian cells (J774 murine macrophages). These promising results make the title organoruthenium compounds good lead candidates for further developments towards potential antitrypanosomal organometallic drugs. PMID:22138896

  2. Novel aldehyde and thiosemicarbazone derivatives: Synthesis, spectroscopic characterization, structural studies and molecular docking studies

    NASA Astrophysics Data System (ADS)

    Karakurt, Tuncay; Tahtaci, Hakan; Subasi, Nuriye Tuna; Er, Mustafa; Ağar, Erbil

    2016-12-01

    In this study our purpose is that, synthesis and characterization of compounds containing the aldehyde and thiosemicarbazone groups and comparison of the theoretical results with the experimental results. The structures of all synthesized compounds were elucidated by IR, 1H NMR, 13C NMR, elemental analyses techniques. The structure of compound (4) (C9H8N4O2S) was also elucidated by X-ray diffraction analysis. In addition, the theoretical IR spectrum, 1H NMR and 13C NMR chemical shift values, frontier molecular orbital values (FMO) of these molecules were analyzed by using Becke-3- Lee-Yang-Parr (B3LYP) method with LanL2DZ basis set. Finally, molecular docking studies were performed on synthesized compounds using the 4DKI beta-lactam protein structure to determine the potential binding mode of inhibitors.

  3. Novel ruthenium(II) cyclopentadienyl thiosemicarbazone compounds with antiproliferative activity on pathogenic trypanosomatid parasites.

    PubMed

    Fernández, Mariana; Arce, Esteban Rodríguez; Sarniguet, Cynthia; Morais, Tânia S; Tomaz, Ana Isabel; Azar, Claudio Olea; Figueroa, Roberto; Diego Maya, J; Medeiros, Andrea; Comini, Marcelo; Helena Garcia, M; Otero, Lucía; Gambino, Dinorah

    2015-12-01

    Searching for new prospective antitrypanosomal agents, three novel Ru(II)-cyclopentadienyl compounds, [Ru(η(5)-C5H5)(PPh3)L], with HL=bioactive 5-nitrofuryl containing thiosemicarbazones were synthesized and characterized in the solid state and in solution. The compounds were evaluated in vitro on the blood circulating trypomastigote form of Trypanosoma cruzi (Dm28c strain), the infective form of Trypanosoma brucei brucei (strain 427) and on J774 murine macrophages and human-derived EA.hy926 endothelial cells. The compounds were active against both parasites with IC50 values in the micromolar or submicromolar range. Interestingly, they are much more active on T. cruzi than previously developed Ru(II) classical and organometallic compounds with the same bioactive ligands. The new compounds showed moderate to very good selectivity towards the parasites in respect to mammalian cells. The global results point at [RuCp(PPh3)L2] (L2=N-methyl derivative of 5-nitrofuryl containing thiosemicarbazone and Cp=cyclopentadienyl) as the most promising compound for further developments (IC50T. cruzi=0.41μM; IC50T. brucei brucei=3.5μM). Moreover, this compound shows excellent selectivity towards T. cruzi (SI>49) and good selectivity towards T. brucei brucei (SI>6). In order to get insight into the mechanism of antiparasitic action, the intracellular free radical production capacity of the new compounds was assessed by ESR. DMPO (5,5-dimethyl-1-pirroline-N-oxide) spin adducts related to the bioreduction of the complexes and to redox cycling processes were characterized. In addition, DNA competitive binding studies with ethidium bromide by fluorescence measurements showed that the compounds interact with this biomolecule.

  4. Gold(III) complexes with ONS-Tridentate thiosemicarbazones: Toward selective trypanocidal drugs.

    PubMed

    Rettondin, Andressa R; Carneiro, Zumira A; Gonçalves, Ana C R; Ferreira, Vanessa F; Oliveira, Carolina G; Lima, Angélica N; Oliveira, Ronaldo J; de Albuquerque, Sérgio; Deflon, Victor M; Maia, Pedro I S

    2016-09-14

    Tridentate thiosemicarbazone ligands with an ONS donor set, H2L(R) (R = Me and Et) were prepared by reactions of 1-phenyl-1,3-butanedione with 4-R-3-thiosemicarbazides. H2L(R) reacts with Na[AuCl4]·2H2O in MeOH in a 1:1 M ratio under formation of green gold(III) complexes of composition [AuCl(L(R))]. These compounds represent the first examples of gold(III) complexes with ONS chelate-bonded thiosemicarbazones. The in vitro anti-Trypanosoma cruzi activity against both trypomastigote and amastigote forms (IC50try/ama) of CL Brener strains as well as the cytotoxicity against LLC-MK2 cells of the free ligands and complexes was evaluated. The complex [AuCl(L(Me))] was found to be more active and more selective than its precursor ligand and the standard drug benznidazole with a SItry/ama value higher than 200, being considered as a lead candidate for Chagas disease treatment. Moreover the in vitro activity against the replicative amastigote form (IC50ama) of T. cruzi was additionally investigated revealing that [AuCl(L(Me))] was also more potent than benznidazole still with a similar selectivity index. Finally, docking studies showed that free ligands and complexes interact with the same residues of the parasite protease cruzain but with different intensities, suggesting that this protease could be a possible target for the trypanocidal action of the obtained compounds.

  5. Rhenium(I) tricarbonyl compounds of bioactive thiosemicarbazones: Synthesis, characterization and activity against Trypanosoma cruzi.

    PubMed

    Rodríguez Arce, Esteban; Machado, Ignacio; Rodríguez, Belén; Lapier, Michel; Zúñiga, María Carolina; Maya, Juan Diego; Olea Azar, Claudio; Otero, Lucía; Gambino, Dinorah

    2017-05-01

    American Trypanosomiasis is a chronic infection discovered and described in 1909 by the Brazilian scientist Carlos Chagas. It is caused by the protozoan parasite Trypanosoma cruzi. Although it affects about 10million people in Latin America, the current chemotherapy is still inadequate. The discovery of new drugs is urgently needed. Our group is focused on the development of prospective metal-based drugs mainly based on bioactive ligands and pharmacologically interesting metal ions. In this work three new rhenium(I) tricarbonyl compounds fac-[Re(I)(CO)3Br(HL)] where HL=5-nitrofuryl containing thiosemicarbazones were synthesized and fully characterized in solution and in the solid state. The in vitro evaluation of the compounds on T. cruzi trypomastigotes (Dm28c strain) showed that the Re(I) compounds are 8 to 15 times more active than the reference drug Nifurtimox and show a 4 to 17 fold increase in activity in respect to the free (HL) ligands. Obtained compounds also show good selectivity indexes (IC50 endothelial cells Ea.hy926/IC50 T. cruzi (Dm28c tripomastigotes)). (1)H NMR and MS studies, performed with time, showed that the fac-[Re(CO)3Br(HL)] species convert into the dimers [Re2(CO)6(L)2] in solution. Crystal structure of [Re(I)2(CO)6(L2)2], the product of complexes' dimerization, was solved. Related to the mechanism of action, the studied compounds do not generate radical oxygen species in the parasite (as 5-nitrofuryl derived thiosemicarbazones do) probably due to the unfavorable nitro reduction potential of the generated dimeric species. On the contrary, the compounds produce a decrease of the oxygen consumption rate of the parasites, maybe inhibiting their mitochondrial respiration.

  6. G2/M Cell Cycle Arrest and Tumor Selective Apoptosis of Acute Leukemia Cells by a Promising Benzophenone Thiosemicarbazone Compound

    PubMed Central

    Cabrera, Maia; Gomez, Natalia; Remes Lenicov, Federico; Echeverría, Emiliana; Shayo, Carina; Moglioni, Albertina; Fernández, Natalia; Davio, Carlos

    2015-01-01

    Anti-mitotic therapies have been considered a hallmark in strategies against abnormally proliferating cells. Focusing on the extensively studied family of thiosemicarbazone (TSC) compounds, we have previously identified 4,4’-dimethoxybenzophenone thiosemicarbazone (T44Bf) as a promising pharmacological compound in a panel of human leukemia cell lines (HL60, U937, KG1a and Jurkat). Present findings indicate that T44Bf-mediated antiproliferative effects are associated with a reversible chronic mitotic arrest caused by defects in chromosome alignment, followed by induced programmed cell death. Furthermore, T44Bf selectively induces apoptosis in leukemia cell lines when compared to normal peripheral blood mononuclear cells. The underlying mechanism of action involves the activation of the mitochondria signaling pathway, with loss of mitochondrial membrane potential and sustained phosphorylation of anti-apoptotic protein Bcl-xL as well as increased Bcl-2 (enhanced phosphorylated fraction) and pro-apoptotic protein Bad levels. In addition, ERK signaling pathway activation was found to be a requisite for T44Bf apoptotic activity. Our findings further describe a novel activity for a benzophenone thiosemicarbazone and propose T44Bf as a promising anti-mitotic prototype to develop chemotherapeutic agents to treat acute leukemia malignancies. PMID:26360247

  7. Copper(II) complexes with 2-pyridineformamide-derived thiosemicarbazones: Spectral studies and toxicity against Artemia salina

    NASA Astrophysics Data System (ADS)

    Ferraz, Karina O.; Wardell, Solange M. S. V.; Wardell, James L.; Louro, Sonia R. W.; Beraldo, Heloisa

    2009-07-01

    The copper(II) complexes [Cu(H2Am4DH)Cl 2] ( 1), [Cu(H2Am4Me)Cl 2] ( 2), [Cu(H2Am4Et)Cl 2] ( 3) and [Cu(2Am4Ph)Cl] ( 4) with 2-pyridineformamide thiosemicarbazone (H2Am4DH) and its N(4)-methyl (H2Am4Me), N(4)-ethyl (H2Am4Et) and N(4)-phenyl (H2Am4Ph) derivatives were studied by means of infrared and EPR spectral techniques. The crystal structure of 4 was determined. The studied compounds proved to be toxic to Artemia salina, suggesting that they could present cytotoxic activity against solid tumors. Among the free thiosemicarbazones H2Am4Ph presented higher toxicity than all other compounds, which showed comparable effects. In the case of complexes 2 and 3 toxicity is probably attributable to the complex as an entity or to a synergistic effect involving the thiosemicarbazone and copper. H2Am4Ph and complexes 2 and 3 revealed to be the most promising compounds as potential antineoplasic agents.

  8. Molecular and supramolecular properties of nitroaromatic thiosemicarbazones: Synthesis, spectroscopy, X-ray structure elucidation and DFT calculations

    NASA Astrophysics Data System (ADS)

    Dias, L. C.; de Lima, G. M.; Pinheiro, C. B.; Nascimento, M. A. C.; Bitzer, R. S.

    2017-03-01

    The reactions of 6-nitropiperonal with H2Nsbnd NHsbnd C(S)sbnd NHR, R = Me, Et, Ph or H, afforded four nitroaromatic thiosemicarbazones 1-4, respectively. 1-4 were characterized by elemental analysis (CHN), FTIR, and 1H and 13C{1H} NMR spectroscopy. In addition, the crystal structures of 2 and 3 were determined by single-crystal X-ray diffraction. Our X-ray structural results have shown that the nitropiperonal and thiosemicarbazone moieties exhibit an almost coplanar arrangement for both 2 and 3. Moreover, they establish 2-D networks along the [111] base vector by means of classical and nonclassical hydrogen bonds. Electronic and spectroscopic properties of 1-4 were investigated at the DFT B3LYP/6-311G** level of calculation. The Cdbnd S group of 1-4 constitutes a nucleophilic region, whereas the NO2 group defines an electrophilic centre, as expected. Furthermore, a DFT vibrational analysis of 4 allowed a reliable assignment of the thiosemicarbazone-based vibrations. Also, a good agreement between theoretical and experimental 13C chemical shift values was obtained for 1-4.

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

    PubMed

    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.

  10. Half-sandwich ruthenium-arene complexes with thiosemicarbazones: Synthesis and biological evaluation of [(η6-p-cymene)Ru(piperonal thiosemicarbazones)Cl]Cl complexes

    PubMed Central

    Dourth, Deidra; Shaloski, Michael; Didion, Jacob; Thessing, Jeffrey; Woods, Jason; Crowell, Vernon; Gerasimchuk, Nikolay; Gonzalez-Sarrías, Antonio; Seeram, Navindra P.

    2011-01-01

    The synthesis and characterization of a number of organometallic ruthenium(II) complexes containing a series of bidentate thiosemicarbazone ligands derived from piperonal is reported. The structure of compounds have been confirmed by spectroscopic analysis (IR and NMR) as well as X-ray crystallographic analysis of [(η6-p-cymene)Ru(pPhTSC)Cl]Cl (4) (pPhTSC is piperonal-N(4)-phenylthiosemicarbazone). The interaction of the complexes ([(η6-p-cymene)Ru(pEtTSC)Cl]Cl) (3) (pEtTSC is piperonal-N(4)-ethylthiosemicarbazone) and 4 with calf thymus DNA, human serum albumin (HSA) and pBR322 plasmid DNA were studied by spectroscopic, gel electrophoresis and hydrodynamic methods. The apparent binding constant for the interaction with DNA was determined to be 3.97 × 103 M−1 and 4.07 × 103 M−1 at 293 K for 3 and 4 respectively. The complexes bind strongly to HSA with binding constants of 2.94 × 104 M−1 and 12.2 × 104 M−1 at 296 K for 3 and 4 respectively. The in vitro anticancer activity of 3 and 4 has been evaluated against two human colon cancer cell line (HCT-116 and Caco-2) with IC50 values in the range 26 – 150 µM. Both 3 and 4 show good activity as a catalytic inhibitor of human topoisomerase II at concentrations as low as 20 µM. The proficiency of 3 and 4 to act as antibacterial agents was also evaluated against six pathogenic bacterial strains with the best activity seen against Gram-positive strains. PMID:21666776

  11. Synthesis, Characterization, Electrochemical Studies, and In Vitro Antibacterial Activity of Novel Thiosemicarbazone and Its Cu(II), Ni(II), and Co(II) Complexes

    PubMed Central

    Khan, Salman A.; Asiri, Abdullah M.; Al-Amry, Khalid; Malik, Maqsood Ahmad

    2014-01-01

    Metal complexes were prepared by the reaction of thiosemicarbazone with CuCl2, NiCl2, CoCl2, Cu(OAc)2, Ni(OAc)2, and Co(OAc)2. The thiosemicarbazone coordinates to metal through the thionic sulfur and the azomethine nitrogen. The thiosemicarbazone was obtained by the thiosemicarbazide with 3-acetyl-2,5-dimethylthiophene. The identities of these compounds were elucidated by IR, 1H, 13C-NMR, and GC-MS spectroscopic methods and elemental analyses. The antibacterial activity of these compounds was first tested in vitro by the disc diffusion assay against two Gram-positive and two Gram-negative bacteria, and then the minimum inhibitory concentration (MIC) was determined by using chloramphenicol as reference drug. The results showed that compound 1.1 is better inhibitor of both types of tested bacteria as compared to chloramphenicol. PMID:24523641

  12. Supramolecular interactions in biologically relevant compounds. 2-Pyrazineformamide thiosemicarbazones and some products of their cyclization

    NASA Astrophysics Data System (ADS)

    Castiñeiras, Alfonso; García-Santos, Isabel; Nogueiras, Silvia; Rodríguez-González, Iria; Rodríguez-Riobó, Raúl

    2014-09-01

    Reaction of 2-cyanopyrazine with thiosemicarbazide or N-methylthiosemicarbazide afforded the (Z)-2-(amino(pyrazin-2-yl)methylene)hydrazinecarbothioamide (HPzAm4DH) and (Z)-2-(amino(pyrazin-2-yl)methylene)-N-methylhydrazine carbothioamide (HPzAm4M), respectively. (2Z,N‧E)-N‧-(4-Oxothiazolidin-2-ylidene)pyrazine-2-carbohydrazonamide (HPzAmot, 5) and (2Z,N‧E)-N‧-(3-methyl-4-oxothiazolidin-2-ylidene)pyrazine-2-carbohydrazonamide (MPzAmot, 7) have been synthesized from these thiosemicarbazones with chloroacetic or bromoacetic acids, using a conventional synthetic methodology and microwave-assisted organic reaction enhancement. The crystal structures of the thiosemicarbazones and their solvates [HPzAm4DHṡ1/2 MeOH (1), HPzAm4DHṡH2O (2), HPzAm4M (3), HPzAm4Mṡ2H2O (4)] and the 1,3-thiazolidin-4-ones (5 and 7) have been studied by X-ray diffractometry. All of the compounds were characterized by elemental analysis, mass spectrometry, FT-IR and 1H and 13C NMR spectroscopy. Several by-products have also been isolated in a crystalline form, namely 3-((Z,E)-N‧-(4-oxothiazolidin-2-ylidene)carbamohydrazonium-yl)pyrazin-1-ium dibromide monohydrate, (H3PzAmot)Br2ṡH2O (6), 2-((5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl)thio)acetic acid, (H2Pz124ttAc) (8), 2-amino-5-(pyrazin-2-yl)-1,3,4-thiadiazol-3-ium chloride monohydrate, (HPz134tda)ClṡH2O (9), and 2-(methylamino)-5-(pyrazin-2-yl)-1,3,4-thiadiazol-3-ium chloride N-methyl-5-(pyrazin-2-yl)-1,3,4-thiadiazol-2-amine solvate, (HMPz134tda)Clṡ(MPz134tda) (10). The structures of these compounds were also analyzed by X-ray diffractometry. The microwave-assisted organic reaction method for synthesis is easy, convenient, and ecofriendly when compared to the traditional synthetic methods. Crystal analysis revealed that the compounds have extended 3D supramolecular networks through high levels of H-bonding and weak molecular interactions between the molecular moieties and solvent molecules. The novel synthons, which are

  13. Identification of Semicarbazones, Thiosemicarbazones and Triazine Nitriles as Inhibitors of Leishmania mexicana Cysteine Protease CPB

    PubMed Central

    Schröder, Jörg; Noack, Sandra; Marhöfer, Richard J.; Mottram, Jeremy C.; Coombs, Graham H.; Selzer, Paul M.

    2013-01-01

    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. PMID:24146999

  14. Benzaldehyde Thiosemicarbazone Derived from Limonene Complexed with Copper Induced Mitochondrial Dysfunction in Leishmania amazonensis

    PubMed Central

    Britta, Elizandra Aparecida; Barbosa Silva, Ana Paula; Ueda-Nakamura, Tânia; Dias-Filho, Benedito Prado; Silva, Cleuza Conceição; Sernaglia, Rosana Lázara; Nakamura, Celso Vataru

    2012-01-01

    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 IC50 concentrations of 3.8 and 9.5 µM, respectively, with 72 h of incubation. Intracellular amastigotes were inhibited by the compound, with an IC50 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. PMID:22870222

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Spectroscopic analysis, AIM, NLO and VCD investigations of acetaldehyde thiosemicarbazone using quantum mechanical simulations

    NASA Astrophysics Data System (ADS)

    Moorthy, N.; Prabakar, P. C. Jobe; Ramalingam, S.; Govindarajan, M.; Gnanamuthu, S. Joshua; Pandian, G. V.

    2016-08-01

    The prepared Acetaldehyde thiosemicarbazone (ATSC) have been investigated by both the experimental and theoretical methods; through this work, the essentiality of elucidation of molecular fragments source linear and non-linear optical properties was explored. The stability of the structure and entire calculations have been performed on HF and B3LYP methods with 6-311++G(d,p) level of basis set. The Mulliken charge profile, electronic, optical and hyper polarizability analyses have been carried out in order to evaluate nonlinear optical (NLO) performance of the present compound. The exact optical location of the ATSC was determined by executing UV-Visible calculations on TDSCF method. The existence of the molecular group for the inducement and tuning of NLO properties were thoroughly investigated by performing fundamental vibrational investigation. The optical energy transformation among frontier molecular levels has been described in UV-Visible region. The Gibbs energy coefficient of thermodynamic functions was monitored in different temperature and it was found constant irrespective of temperatures. The appearance of different chemical environment of H and C was monitored from the 1H and 13C NMR spectra. The vibrational optical polarization characteristics with respect to molecular composition in the compound have been studied by VCD spectrum. The bond critical point, Laplacian of electron density, electron kinetic energy density and total electron energy density have calculated and analysed using AIM study.

  17. Synthesis and cytotoxic activity of N-substituted thiosemicarbazones of 3-(3,4-methylenedioxy)phenylpropanal.

    PubMed

    Joselice e Silva, M; Alves, A J; Do Nascimento, S C

    1998-03-01

    Five new N-substituted thiosemicarbazones of 3-(3,4-methylenedioxy)phenylpropanal were synthesized. Safrole, a natural product obtained from sassafras oil (Ocotea pretiosa), was oxidized to alcohol using BH3-THF and H2O2, followed by oxidation to aldehyde using pyridinium dichromate (PDC) and condensation with five N-substituted derivatives of thiosemicarbazide. Tests were performed to evaluate the cytotoxic activity with continuous chain KB cells (epidermoide carcinoma of the floor of the mouth). Compounds 5 and 6 showed IC50 values of 1.5 and 4.6 micrograms/ml, respectively.

  18. Structural requirement(s) of N-phenylthioureas and benzaldehyde thiosemicarbazones as inhibitors of melanogenesis in melanoma B 16 cells.

    PubMed

    Thanigaimalai, P; Hoang, Tuan Anh Le; Lee, Ki-Cheul; Bang, Seong-Cheol; Sharma, Vinay K; Yun, Cheong-Yong; Roh, Eunmiri; Hwang, Bang-Yeon; Kim, Youngsoo; Jung, Sang-Hun

    2010-05-01

    In order to define the structural requirements of phenylthiourea (PTU), a series of thiourea and thiosemicarbazone analogs were prepared and evaluated as inhibitors of melanogenesis in melanoma B16 cells. The most potent analog was 2-(4-tert-butylbenzylidene)hydrazinecarbothioamide (1u) with an IC(50) value of 2.7 microM in inhibition of melanogenesis. The structure for potent inhibitory activity of these derivatives are required with the direct connection of pi-planar structure to thiourea without steric hinderance in PTU derivatives and the hydrophobic substituent at para position in case of semicarbazones.

  19. Targeting triple negative breast cancer cells by N3-substituted 9,10-Phenanthrenequinone thiosemicarbazones and their metal complexes

    NASA Astrophysics Data System (ADS)

    Afrasiabi, Zahra; Stovall, Preston; Finley, Kristen; Choudhury, Amitava; Barnes, Charles; Ahmad, Aamir; Sarkar, Fazlul; Vyas, Alok; Padhye, Subhash

    2013-10-01

    Novel N3-substituted 9,10-Phenanthrenequinone thiosemicarbazones and their copper, nickel and palladium complexes are structurally characterized and reported along with the single crystal X-ray structures of three ligands and one nickel complex. All compounds were evaluated for their antiproliferative potential against Triple Negative Breast Cancer (TNBC) cells which have poor prognosis and no effective drugs to treat with. All compounds exhibited antiproliferative activity against these cells. Among the metal complexes evaluated, redox active copper complexes were found to be more potent. The possible mechanism for such enhanced activity can be attributed to the generation of oxidative stress, which was amenable for targeting through metal complexation.

  20. New Iminodiacetate-Thiosemicarbazone Hybrids and Their Copper(II) Complexes Are Potential Ribonucleotide Reductase R2 Inhibitors with High Antiproliferative Activity.

    PubMed

    Zaltariov, Mirela F; Hammerstad, Marta; Arabshahi, Homayon J; Jovanović, Katarina; Richter, Klaus W; Cazacu, Maria; Shova, Sergiu; Balan, Mihaela; Andersen, Niels H; Radulović, Siniša; Reynisson, Jóhannes; Andersson, K Kristoffer; Arion, Vladimir B

    2017-03-20

    As ribonucleotide reductase (RNR) plays a crucial role in nucleic acid metabolism, it is an important target for anticancer therapy. The thiosemicarbazone Triapine is an efficient R2 inhibitor, which has entered ∼20 clinical trials. Thiosemicarbazones are supposed to exert their biological effects through effectively binding transition-metal ions. In this study, six iminodiacetate-thiosemicarbazones able to form transition-metal complexes, as well as six dicopper(II) complexes, were synthesized and fully characterized by analytical, spectroscopic techniques (IR, UV-vis; (1)H and (13)C NMR), electrospray ionization mass spectrometry, and X-ray diffraction. The antiproliferative effects were examined in several human cancer and one noncancerous cell lines. Several of the compounds showed high cytotoxicity and marked selectivity for cancer cells. On the basis of this, and on molecular docking calculations one lead dicopper(II) complex and one thiosemicarbazone were chosen for in vitro analysis as potential R2 inhibitors. Their interaction with R2 and effect on the Fe(III)2-Y· cofactor were characterized by microscale thermophoresis, and two spectroscopic techniques, namely, electron paramagnetic resonance and UV-vis spectroscopy. Our findings suggest that several of the synthesized proligands and copper(II) complexes are effective antiproliferative agents in several cancer cell lines, targeting RNR, which deserve further investigation as potential anticancer drugs.

  1. Improved antiparasitic activity by incorporation of organosilane entities into half-sandwich ruthenium(II) and rhodium(III) thiosemicarbazone complexes.

    PubMed

    Adams, Muneebah; de Kock, Carmen; Smith, Peter J; Land, Kirkwood M; Liu, Nicole; Hopper, Melissa; Hsiao, Allyson; Burgoyne, Andrew R; Stringer, Tameryn; Meyer, Mervin; Wiesner, Lubbe; Chibale, Kelly; Smith, Gregory S

    2015-02-07

    A series of ferrocenyl- and aryl-functionalised organosilane thiosemicarbazone compounds was obtained via a nucleophilic substitution reaction with an amine-terminated organosilane. The thiosemicarbazone (TSC) ligands were further reacted with either a ruthenium dimer [(η(6-i)PrC6H4Me)Ru(μ-Cl)Cl]2 or a rhodium dimer [(Cp*)Rh(μ-Cl)Cl]2 to yield a series of cationic mono- and binuclear complexes. The thiosemicarbazone ligands, as well as their metal complexes, were characterised using NMR and IR spectroscopy, and mass spectrometry. The molecular structure of the binuclear ruthenium(ii) complex was determined by single-crystal X-ray diffraction analysis. The thiosemicarbazones and their complexes were evaluated for their in vitro antiplasmodial activities against the chloroquine-sensitive (NF54) and chloroquine-resistant (Dd2) Plasmodium falciparum strains, displaying activities in the low micromolar range. Selected compounds were screened for potential β-haematin inhibition activity, and it was found that two Rh(iii) complexes exhibited moderate to good inhibition. Furthermore, the compounds were screened for their antitrichomonal activities against the G3 Trichomonas vaginalis strain, revealing a higher percentage of growth inhibition for the ruthenium and rhodium complexes over their corresponding ligand.

  2. Synthesis, Characterization and Molecular Structures of some Bismuth(III) Complexes with Thiosemicarbazones and Dithiocarbazonic Acid Methylester Derivatives with Activity against Helicobacter Pylori

    PubMed Central

    Diemer, Rolf; Dittes, Uwe; Nuber, Bernhard; Seifried, Volker; Opferkuch, Wolfgang

    1995-01-01

    The reactions of bismuth(III) nitrate pentahydrate and bismuth(III) chloride with heterocyclic thiosemicarbazones and derivatives of dithiocarbazonic acid methylester were used to synthesize the respective bismuth(III) complexes, which could be divided into five groups D-H because of their stoichiometrical properties and their molecular structures. The molecular structure and the near coordination sphere of the bismuth(III) central atom of four representative compounds were determined by single-crystal X-ray studies. Bis[1-azepanyl-4-(2-pyridyl)-2,3-diazapenta-1,3-diene-1-thiolato-N′,N3,S]bismuth(III) nitrate (5) belongs to group D. The two tridentate ligands and the nitrate ion surround the bismuth atom. The best description of the coordination sphere appears to be that of a distorted trigonal dodecahedron with one position occupied by the lone pair of the bismuth atom. Bis[1-azepanyl-4-(2-thienyl)-2,3-diazapenta-1,3-diene-1-thiolato-N3,S]bismuth(III) nitrate (9) is assigned to complex type E. Here, two deprotonated ligand molecules are coordinated to the bismuth(III) central atom as bidentate ligands. The structure of this complex can best be described as a distorted trigonal antiprism with a five-coordinated central atom. The two triangular faces are formed by the atoms S(4), N(6), O(11) and S(3), N(4) and the lone pair of the central atom. The two chelate rings are almost perpendicular to each other. Complex molecules of group F form dimeric units with bichloro-bridged bismuth atoms. The structure of di-μ-chlorobis[1-azepanyl-4-(2-pyridyl)-2,3-diazapenta-1,3-diene-1-thiolato-N′,N3,S-chloro]dibismuth(III) (15) can be described as two six-coordinated bismuth atoms, which are bound together via two bridging chlorine atoms. The two bismuth atoms Bi(1) and Bi(1a) and the two bridging chlorine atoms Cl(2) and Cl(2a) form the Bi2Cl2 plane. The two tridentate ligand molecules coordinate via the same atoms as shown in complex 5. In addition, they form two parallel

  3. New Oxidovanadium Complexes Incorporating Thiosemicarbazones and 1, 10-Phenanthroline Derivatives as DNA Cleavage, Potential Anticancer Agents, and Hydroxyl Radical Scavenger.

    PubMed

    Ying, Peng; Zeng, Pengfei; Lu, Jiazheng; Chen, Hongyuan; Liao, Xiangwen; Yang, Ning

    2015-10-01

    Four novel oxidovanadium(IV) complexes, [VO(hntdtsc)(PHIP)] (1) (hntdtsc = 2-hydroxy-1-naphthaldehyde thiosemicarbazone, PHIP= 2-phenyl-imidazo[4,5-f]1,10-phenanthroline), [VO(hntdtsc)(DPPZ)](2)(DPPZ= dipyrido[3,2-a:2',3'-c]phenazine), [VO(satsc)(PHIP)](3) (satsc=salicylaldehyde thiosemicarbazone), and [VO(satsc)(DPPZ)](4), have been prepared and characterized. The chemical nuclease activities and photocleavage reactions of the complexes were tested. All four complexes can efficiently cleave pBR322 DNA, and complex 1 has the best cleaving ability. The antitumor properties of these complexes were examined with three different tumor cell lines using MTT assay. Their antitumor mechanism has been analyzed using cell cycle analysis, fluorescence microscopy of apoptosis, and Annexin V-FITC/PI assay. The results showed that the growth of human neuroblastoma (SH-SY5Y, SK-N-SH) and human breast adenocarcinoma (MCF-7) cells were inhibited significantly with very low IC50 values. Complex 1 was found to be the most potent antitumor agent among the four complexes. It can cause G0/G1 phase arrest of the cell cycle and exhibited significant induced apoptosis in SK-N-SH cells and displayed typical morphological apoptotic characteristics. In addition, they all displayed reasonable abilities to scavenge hydroxyl radical, and complex 1 was the best inhibitor.

  4. Platinum-based complexes of bioactive 3-(5-nitrofuryl)acroleine thiosemicarbazones showing anti-Trypanosoma cruzi activity.

    PubMed

    Vieites, Marisol; Otero, Lucía; Santos, Diego; Olea-Azar, Claudio; Norambuena, Ester; Aguirre, Gabriela; Cerecetto, Hugo; González, Mercedes; Kemmerling, Ulrike; Morello, Antonio; Diego Maya, Juan; Gambino, Dinorah

    2009-03-01

    Eight new platinum(II) complexes with 3-(5-nitrofuryl)acroleine thiosemicarbazones showing anti-trypanosomal activity were synthesized, characterized and in vitro evaluated. Most of the complexes showed IC(50) values in the micromolar range against two different strains of Trypanosoma cruzi, causative agent of Chagas disease (American Trypanosomiasis). In addition, most of the newly developed complexes, together with the analogous platinum 5-nitrofuraldehyde containing thiosemicarbazones previously reported, resulted more active than the reference trypanocidal drug nifurtimox on the infective trypomastigote form of the parasite. Their capacity to produce free radicals that could lead to parasite death was evaluated by ESR experiments in the parasite and by respiration measurements. Compounds were tested for their DNA interaction ability. Results showed that some of the compounds could act as dual inhibitors in the parasite, through production of toxic free radicals and interaction with DNA. All the results were compared with those previously reported for the free ligands, the analogous palladium(II) compounds and the previously reported series of platinum(II) compounds.

  5. α(N)-Heterocyclic Thiosemicarbazones: Iron Chelators That Are Promising for Revival of Gallium in Cancer Chemotherapy.

    PubMed

    Cao, Shuhong; Chen, Xiahui; Chen, Ligen; Chen, Jingwen

    2016-03-10

    The metal-based drugs have gained increasing attention in the fight against cancer. Ga(III) in the form of inorganic salts has demonstrated efficacy in the treatment of a number of malignancies in experimental animals and humans, and has therefore attracted considerable pharmaceutical interest. However, the poor hydrolytic stability of Ga(III) in physiological medium owing to its property of hard Lewis acid prevents its widespread use in systemic cancer chemotherapy. Complexation of suitable chelators capable of stabilising Ga(III) against hydrolysis affords an opportunity for overcoming this drawback. Thiosemicarbazone (TSC) derivatives, a class of well-studied iron chelators featuring softer donor sulfur, also were evaluated to possess antineoplastic activities in an arrary of tumour cell lines. The structural modifications can affect the activities of TSCs, and related structure-activity relationships (SAR) have been studied over these years. Combination of Ga(III) and TSCs that are both pharmaceutically active has proved to exert synergistic effects of each component in one compound in most cases, and may produce more potent Ga(III) drugs. In this review, the SAR of α(N)-heterocyclic thiosemicarbazone (HCT) analogues, a family of TSCs, were scrupulously surveyed, and the effect of Ga(III) complexation on their anticancer activity sparsely reported in literature was comparatively examined, in order to stimulate further advances in the field of gallium-based anticancer drugs.

  6. Biologically active thiosemicarbazone Fe chelators and their reactions with ferrioxamine B and ferric EDTA; a kinetic study.

    PubMed

    Bernhardt, Paul V; Martínez, Manuel; Rodríguez, Carlos; Vazquez, Marta

    2012-02-21

    The Fe(III) abstraction from Fe(III)/DFO and Fe(III)/EDTA complex systems by thiosemicarbazone ligands derived from 2-acetylpyridine has been studied from a kinetico-mechanistic perspective at relevant pH conditions and at varying temperatures and buffer solutions. The reactions have been found to be extremely dependent on the dominant E/Z isomeric form of the TSC ligands present in the reaction medium. Consequently the isomerisation processes occurring on the free ligands have also been monitored under equivalent conditions. The isomerisation process is found to be acid dependent, despite the absence of protonation under the conditions used, and presumably proceeds via an azo-type tautomer of the ligand. In all cases the existence of outer-sphere interaction processes has been established, both promoting the reactions and producing dead-end complexes. The better oriented forms of the ligands (EZ thiolate) have been found to react faster with the [Fe(HDFO)](+) complex, although for mono-N(4) substituted thiosemicarbazones the process is retarded by the formation of a dead-end outer-sphere complex. A comparison with the abstraction of Fe(III) from [Fe(EDTA)(H(2)O)](-) has also been conducted with significant differences in the kinetic features that implicate keystone outer-sphere interactions which dominate reactivity, even with isomeric forms that are not the best suited for direct complexation.

  7. Thiosemicarbazones and Phthalyl-Thiazoles compounds exert antiviral activity against yellow fever virus and Saint Louis encephalitis virus.

    PubMed

    Pacca, Carolina Colombelli; Marques, Rafael Elias; Espindola, José Wanderlan P; Filho, Gevânio B O Oliveira; Leite, Ana Cristina Lima; Teixeira, Mauro Martins; Nogueira, Mauricio L

    2017-03-01

    Arboviruses, arthropod-borneviruses, are frequency associated to human outbreak and represent a serious health problem. The genus Flavivirus, such as Yellow Fever Virus (YFV) and Saint Louis Encephalitis Virus (SLEV), are important pathogens with high morbidity and mortality worldwide. In Brazil, YFV is maintained in sylvatic cycle, but many cases are notified annually, despite the efficiency of vaccine. SLEV causes an acute encephalitis and is widely distributed in the Americas. There is no specific antiviral drugs for these viruses, only supporting treatment that can alleviate symptoms and prevent complications. Here, we evaluated the potential anti-YFV and SLEV activity of a series of thiosemicarbazones and phthalyl-thiazoles. Plaque reduction assay, flow cytometry, immunofluorescence and cellular viability were used to test the compounds in vitro. Treated cells showed efficient inhibition of the viral replication at concentrations that presented minimal toxicity to cells. The assays showed that phthalyl-thiazole and phenoxymethyl-thiosemicarbazone reduced 60% of YFV replication and 75% of SLEV replication.

  8. Vibrational, NMR and UV-Visible spectroscopic investigation, VCD and NLO studies on Benzophenone thiosemicarbazone using computational calculations

    NASA Astrophysics Data System (ADS)

    Moorthy, N.; Jobe Prabakar, P. C.; Ramalingam, S.; Periandy, S.; Parasuraman, K.

    2016-04-01

    In order to explore the unbelievable NLO property of prepared Benzophenone thiosemicarbazone (BPTSC), the experimental and theoretical investigation has been made. The theoretical calculations were made using RHF and CAM-B3LYP methods at 6-311++G(d,p) basis set. The title compound contains Cdbnd S ligand which helps to improve the second harmonic generation (SHG) efficiency. The molecule has been examined in terms of the vibrational, electronic and optical properties. The entire molecular behavior was studied by their fundamental IR and Raman wavenumbers and was compared with the theoretical aspect. The molecular chirality has been studied by performing vibrational circular dichroism (circularly polarized infrared radiation). The Mulliken charge levels of the compound ensure the perturbation of atomic charges according to the ligand. The molecular interaction of frontier orbitals emphasizes the modification of chemical properties of the compound through the reaction path. The enormous amount of NLO activity was induced by the Benzophenone in thiosemicarbazone. The Gibbs free energy was evaluated at different temperature and from which the enhancement of chemical stability was stressed. The VCD spectrum was simulated and the optical dichroism of the compound has been analyzed.

  9. Synthesis of thiophene-thiosemicarbazone derivatives and evaluation of their in vitro and in vivo antitumor activities.

    PubMed

    de Oliveira, Jamerson Ferreira; da Silva, Anekécia Lauro; Vendramini-Costa, Débora Barbosa; da Cruz Amorim, Cezar Augusto; Campos, Júlia Furtado; Ribeiro, Amélia Galdino; Olímpio de Moura, Ricardo; Neves, Jorge Luiz; Ruiz, Ana Lúcia Tasca Gois; Ernesto de Carvalho, João; Alves de Lima, Maria do Carmo

    2015-11-02

    A series of thiophene-2-thiosemicarbazones derivatives (5-14) was synthesized, characterized and evaluated for their antitumor activity. They were tested in vitro against human tumor cell lines through the colorimetric method. The results revealed that compounds 7 and 9 were the most effective in inhibiting 50% of the cell growth after 48 h of treatment. As compound 7 showed a potent antiproliferative profile, it has been chosen for further studies in 786-0 cell line by flow cytometry. Treatments with compound 7 (50 μM) induced early phosphatidylserine exposure after 18 h of exposure and this process progressed phosphatidylserine exposure with loss of cell membrane integrity after 24 h of treatment, suggesting a time-dependent cell death process. Regarding the cell cycle profile, no changes were observed after treatment with compound 7 (25 μM), suggesting a mechanism of cell death independent on the cell cycle. The in vivo studies show that compound 7 possess low acute toxicity, being the doses of 30-300 mgKg(-1) chosen for studies in Ehrlich solid tumor model in mice. All doses were able to inhibit tumor development being the lowest one the most effective. Our findings highlight thiophene-2-thiosemicarbazones as a promising class of compounds for further studies concerning new anticancer therapies.

  10. In vitro cytotoxic, antibacterial, antifungal and urease inhibitory activities of some N4- substituted isatin-3-thiosemicarbazones.

    PubMed

    Pervez, Humayun; Iqbal, Mohammad S; Tahir, Muhammad Younas; Nasim, Faiz-ul-Hassan; Choudhary, Muhammad Iqbal; Khan, Khalid Mohammed

    2008-12-01

    A series of 15 previously reported N(4)-substituted isatin-3-thiosemicarbazones 3a-o has been screened for cytotoxic, antibacterial, antifungal and urease inhibitory activities. Compounds 3b, 3e and 3n proved to be active in cytotoxicity assay; 3e exhibited a high degree of cytotoxic activity (LD(50) = 1.10 x 10(-5) M). Compound 3h exhibited significant antibacterial activity against B. subtilis, whereas compounds 3a, 3k and 3l displayed significant antifungal activity against one or more fungal strains i.e. T. longifusus, A. flavus and M. canis. In human urease enzyme inhibition assay, compounds 3g, 3k and 3m proved to be the most potent inhibitors, exhibiting relatively pronounced inhibition of the enzyme. These compounds, being non-toxic, could be potential candidates for orally effective therapeutic agents to treat certain clinical conditions induced by bacterial ureases like H. pylori urease. This study presents the first example of inhibition of urease by isatin-thiosemicarbazones and as such provides a solid basis for further research on such compounds to develop more potent inhibitors.

  11. Evaluation of the Anti-Schistosoma mansoni Activity of Thiosemicarbazones and Thiazoles

    PubMed Central

    de Oliveira, Sheilla Andrade; de Oliveira Filho, Gevânio Bezerra; Moreira, Diogo Rodrigo Magalhaes; Gomes, Paulo André Teixeira; da Silva, Anekécia Lauro; de Barros, Andréia Ferreira; da Silva, Aline Caroline; dos Santos, Thiago André Ramos; Pereira, Valéria Rêgo Alves; Gonçalves, Gabriel Gazzoni Araújo; Brayner, Fábio André; Alves, Luiz Carlos; Wanderley, Almir Gonçalves; Leite, Ana Cristina Lima

    2014-01-01

    Schistosomiasis is a chronic and debilitating disease caused by a trematode of the genus Schistosoma and affects over 207 million people. Chemotherapy is the only immediate recourse for minimizing the prevalence of this disease and involves predominately the administration of a single drug, praziquantel (PZQ). Although PZQ has proven efficacy, there is a recognized need to develop new drugs as schistosomicides since studies have shown that repeated use of this drug in areas of endemicity may cause a temporary reduction in susceptibility in isolates of Schistosoma mansoni. Hydrazones, thiosemicarbazones, phthalimides, and thiazoles are thus regarded as privileged structures used for a broad spectrum of activities and are potential candidates for sources of new drug prototypes. The present study determined the in vitro schistosomicidal activity of 10 molecules containing these structures. During the assays, parameters such motility and mortality, oviposition, morphological changes in the tegument, cytotoxicity, and immunomodulatory activity caused by these compounds were evaluated. The results showed that compounds formed of thiazole and phthalimide led to higher mortality of worms, with a significant decline in motility, inhibition of pairing and oviposition, and a mortality rate of 100% starting from 144 h of exposure. These compounds also stimulated the production of nitric oxide and tumor necrosis factor alpha (TNF-α), thereby demonstrating the presence of immunomodulatory activity. The phthalyl thiazole LpQM-45 caused significant ultrastructural alterations, with destruction of the tegument in both male and female worms. According to the present study, phthalyl thiazole compounds possess antischistosomal activities and should form the basis for future experimental and clinical trials. PMID:24165185

  12. Antibacterial, antifungal and in vitro antileukaemia activity of metal complexes with thiosemicarbazones

    PubMed Central

    Pahontu, Elena; Julea, Felicia; Rosu, Tudor; Purcarea, Victor; Chumakov, Yurie; Petrenco, Petru; Gulea, Aurelian

    2015-01-01

    1-phenyl-3-methyl-4-benzoyl-5-pyrazolone 4-ethyl-thiosemicarbazone (HL) and its copper(II), vanadium(V) and nickel(II) complexes: [Cu(L)(Cl)]·C2H5OH·(1), [Cu(L)2]·H2O (2), [Cu(L)(Br)]·H2O·CH3OH (3), [Cu(L)(NO3)]·2C2H5OH (4), [VO2(L)]·2H2O (5), [Ni(L)2]·H2O (6), were synthesized and characterized. The ligand has been characterized by elemental analyses, IR, 1H NMR and 13C NMR spectroscopy. The tridentate nature of the ligand is evident from the IR spectra. The copper(II), vanadium(V) and nickel(II) complexes have been characterized by different physico-chemical techniques such as molar conductivity, magnetic susceptibility measurements and electronic, infrared and electron paramagnetic resonance spectral studies. The structures of the ligand and its copper(II) (2, 4), and vanadium(V) (5) complexes have been determined by single-crystal X-ray diffraction. The composition of the coordination polyhedron of the central atom in 2, 4 and 5 is different. The tetrahedral coordination geometry of Cu was found in complex 2 while in complex 4, it is square planar, in complex 5 the coordination polyhedron of the central ion is distorted square pyramid. The in vitro antibacterial activity of the complexes against Escherichia coli, Salmonella abony, Staphylococcus aureus, Bacillus cereus and the antifungal activity against Candida albicans strains was higher for the metal complexes than for free ligand. The effect of the free ligand and its metal complexes on the proliferation of HL-60 cells was tested. PMID:25708540

  13. Biophysical characterization and antineoplastic activity of new bis(thiosemicarbazonato) Cu(II) complexes.

    PubMed

    Palma, Elisa; Mendes, Filipa; Morais, Goreti Ribeiro; Rodrigues, Inês; Santos, Isabel Cordeiro; Campello, Maria Paula C; Raposinho, Paula; Correia, Isabel; Gama, Sofia; Belo, Dulce; Alves, Vítor; Abrunhosa, Antero J; Santos, Isabel; Paulo, António

    2017-02-01

    Aiming to explore alternative mechanisms of cellular uptake and cytotoxicity, we have studied a new family of copper(II) complexes (CuL(1)-CuL(4)) with bis(thiosemicarbazone) (BTSC) ligands containing pendant protonable cyclic amines (morpholine and piperidine). Herein, we report on the synthesis and characterization of these new complexes, as well as on their biological performance (cytotoxic activity, cellular uptake, protein and DNA binding), in comparison with the parental Cu(II)ATSM (ATSM=diacetyl-bis(N4-methylthiosemicarbazonate) complex without pendant cyclic amines. The new compounds have been characterized by a range of analytical techniques including ESI-MS, IR spectroscopy, cyclic voltammetry, reverse-phase HPLC and X-ray spectroscopy. In vitro cytotoxicity studies revealed that the copper complexes are cytotoxic, unlike the corresponding ligands, with a similar potency to that of CuATSM. Unlike CuATSM, the new complexes were able to circumvent cisplatin cross-resistance. The presence of the protonable cyclic amines did not lead to an enhancement of the interaction of the complexes with human serum albumin or calf thymus DNA. However, CuL(1)-CuL(4) showed a remarkably augmented cellular uptake compared with CuATSM, as proved by uptake, internalization and externalization studies that were performed using the radioactive congeners (64)CuL(1)-(64)CuL(4). The enhanced cellular uptake of CuL(1)-CuL(4) indicates that this new family of Cu(II)BTSC complexes deserves to be further evaluated in the design of metallodrugs for cancer theranostics.

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

    PubMed

    Chandra, Sulekh; Kumar, Anil

    2007-12-31

    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.

  15. Synthesis, stereochemical, structural and biological studies of some 2,6-diarylpiperidin-4-one N(4‧)-cyclohexyl thiosemicarbazones

    NASA Astrophysics Data System (ADS)

    Sethukumar, A.; Udhaya Kumar, C.; Agilandeshwari, R.; Arul Prakasam, B.

    2013-09-01

    A new series of 2,6-diarylpiperidin-4-one N(4')-cyclohexyl thiosemicarbazones (13-23) were synthesized by corresponding 2,6-diarylpiperidin-4-ones (1-11) reaction with cyclohexyl thiosemicarbazide (12). The chemical structures were confirmed by means of IR, one and two dimensional NMR, Mass spectra and single crystal X-ray diffraction analysis. Compounds 13-23, exist in chair conformation with equatorial orientation of all the substituents at piperidine ring except the methyl group at C-5 of compounds 21-23 oriented at axial disposition to stabilize the chair conformation. Single crystal X-ray structural analysis of compound 18, evidences that the configuration about Cdbnd N double bond is syn to C-5 carbon (E-form). All the synthesized compounds were screened their biological activity.

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

    PubMed

    Gaffer, Hatem E; Khalifa, Mohamed E

    2015-12-09

    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.

  17. Synthesis, antioxidant activities of the nickel(II), iron(III) and oxovanadium(IV) complexes with N2O2 chelating thiosemicarbazones.

    PubMed

    Bal-Demirci, Tülay; Sahin, Musa; Ozyürek, Mustafa; Kondakçı, Esin; Ulküseven, Bahri

    2014-05-21

    The nickel(II), iron(III) and oxovanadium(IV) complexes of the N2O2 chelating thiosemicarbazones were synthesized using 4-hydroxysalicyladehyde-S-methylthiosemicarbazone and R1-substitute-salicylaldehyde (R1: 4-OH, H) in the presence of Ni(II), Fe(III), VO(IV) ions by the template reaction. The structures of the thiosemicarbazone complexes were characterized by FT-IR, (1)H NMR, elemental, ESI-MS and APCI-MS analysis. The synthesized compounds were screened for their antioxidant capacity by using the cupric reducing antioxidant capacity (CUPRAC) method. Trolox equivalent antioxidant capacity (TEAC) of iron(III) complex, 1c, was measured to be higher than that of the other complexes. Other parameters of antioxidant activity (scavenging effects on •OH, O2(•-) and H2O2) of these compounds were also determined. All the compounds have shown encouraging ROS scavenging activities.

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

    PubMed Central

    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

  19. Highly potent anti-proliferative effects of a gallium(III) complex with 7-chloroquinoline thiosemicarbazone as a ligand: synthesis, cytotoxic and antimalarial evaluation.

    PubMed

    Kumar, Kewal; Schniper, Sarah; González-Sarrías, Antonio; Holder, Alvin A; Sanders, Natalie; Sullivan, David; Jarrett, William L; Davis, Krystyn; Bai, Fengwei; Seeram, Navindra P; Kumar, Vipan

    2014-10-30

    A gallium(III) complex with 7-chloroquinoline thiosemicarbazone was synthesized and characterized. The complex proved to be thirty-one times more potent on colon cancer cell line, HCT-116, with considerably less cytotoxicity on non-cancerous colon fibroblast, CCD-18Co, when compared to etoposide. Its anti-malarial potential on 3D7 isolate of Plasmodium falciparum was better than lumefantrine.

  20. Synthesis and characterization of mixed-ligand diimine-piperonal thiosemicarbazone complexes of ruthenium(II): Biophysical investigations and biological evaluation as anticancer and antibacterial agents

    NASA Astrophysics Data System (ADS)

    Beckford, Floyd A.; Thessing, Jeffrey; Shaloski, Michael, Jr.; Canisius Mbarushimana, P.; Brock, Alyssa; Didion, Jacob; Woods, Jason; Gonzalez-Sarrías, Antonio; Seeram, Navindra P.

    2011-04-01

    We have used a novel microwave-assisted method developed in our laboratories to synthesize a series of ruthenium-thiosemicarbazone complexes. The new thiosemicarbazone ligands are derived from benzo[ d][1,3]dioxole-5-carbaldehyde (piperonal) and the complexes are formulated as [(diimine) 2Ru(TSC)](PF 6) 2 (where the TSC is the bidentate thiosemicarbazone ligand). The diimine in the complexes is either 2,2'-bipyridine or 1,10-phenanthroline. The complexes have been characterized by spectroscopic means (NMR, IR and UV-Vis) as well as by elemental analysis. We have studied the biophysical characteristics of the complexes by investigating their anti-oxidant ability as well as their ability to disrupt the function of the human topoisomerase II enzyme. The complexes are moderately strong binders of DNA with binding constants of 10 4 M -1. They are also strong binders of human serum albumin having binding constants on the order of 10 4 M -1. The complexes show good in vitro anticancer activity against human colon cancer cells, Caco-2 and HCT-116 and indeed show some cytotoxic selectivity for cancer cells. The IC 50 values range from 7 to 159 μM (after 72 h drug incubation). They also have antibacterial activity against Gram-positive strains of pathogenic bacteria with IC 50 values as low as 10 μM; little activity was seen against Gram-negative strains. It has been established that all the compounds are catalytic inhibitors of human topoisomerase II.

  1. Copper(II) complexes with highly water-soluble L- and D-proline-thiosemicarbazone conjugates as potential inhibitors of Topoisomerase IIα.

    PubMed

    Bacher, Felix; Enyedy, Éva A; Nagy, Nóra V; Rockenbauer, Antal; Bognár, Gabriella M; Trondl, Robert; Novak, Maria S; Klapproth, Erik; Kiss, Tamás; Arion, Vladimir B

    2013-08-05

    Two proline-thiosemicarbazone bioconjugates with excellent aqueous solubility, namely, 3-methyl-(S)-pyrrolidine-2-carboxylate-2-formylpyridine thiosemicarbazone [L-Pro-FTSC or (S)-H2L] and 3-methyl-(R)-pyrrolidine-2-carboxylate-2-formylpyridine thiosemicarbazone [D-Pro-FTSC or (R)-H2L], have been synthesized and characterized by elemental analysis, one- and two-dimensional (1)H and (13)C NMR spectroscopy, and electrospray ionization mass spectrometry. The complexation behavior of L-Pro-FTSC with copper(II) in an aqueous solution and in a 30% (w/w) dimethyl sulfoxide/water mixture has been studied via pH potentiometry, UV-vis spectrophotometry, electron paramagnetic resonance, (1)H NMR spectroscopy, and spectrofluorimetry. By the reaction of copper(II) acetate with (S)-H2L and (R)-H2L in water, the complexes [Cu(S,R)-L] and [Cu(R,S)-L] have been synthesized and comprehensively characterized. An X-ray diffraction study of [Cu(S,R)-L] showed the formation of a square-pyramidal complex, with the bioconjugate acting as a pentadentate ligand. Both copper(II) complexes displayed antiproliferative activity in CH1 ovarian carcinoma cells and inhibited Topoisomerase IIα activity in a DNA plasmid relaxation assay.

  2. Synthesis of a Sugar-Based Thiosemicarbazone Series and Structure-Activity Relationship versus the Parasite Cysteine Proteases Rhodesain, Cruzain, and Schistosoma mansoni Cathepsin B1

    PubMed Central

    Fonseca, Nayara Cristina; da Cruz, Luana Faria; da Silva Villela, Filipe; do Nascimento Pereira, Glaécia Aparecida; de Siqueira-Neto, Jair Lage; Kellar, Danielle; Suzuki, Brian M.; Ray, Debalina; de Souza, Thiago Belarmino; Alves, Ricardo José; Júnior, Policarpo Ademar Sales; Romanha, Alvaro José; Murta, Silvane Maria Fonseca; McKerrow, James H.; Caffrey, Conor R.; de Oliveira, Renata Barbosa

    2015-01-01

    The pressing need for better drugs against Chagas disease, African sleeping sickness, and schistosomiasis motivates the search for inhibitors of cruzain, rhodesain, and Schistosoma mansoni CB1 (SmCB1), the major cysteine proteases from Trypanosoma cruzi, Trypanosoma brucei, and S. mansoni, respectively. Thiosemicarbazones and heterocyclic analogues have been shown to be both antitrypanocidal and inhibitory against parasite cysteine proteases. A series of compounds was synthesized and evaluated against cruzain, rhodesain, and SmCB1 through biochemical assays to determine their potency and structure-activity relationships (SAR). This approach led to the discovery of 6 rhodesain, 4 cruzain, and 5 SmCB1 inhibitors with 50% inhibitory concentrations (IC50s) of ≤10 μM. Among the compounds tested, the thiosemicarbazone derivative of peracetylated galactoside (compound 4i) was discovered to be a potent rhodesain inhibitor (IC50 = 1.2 ± 1.0 μM). The impact of a range of modifications was determined; removal of thiosemicarbazone or its replacement by semicarbazone resulted in virtually inactive compounds, and modifications in the sugar also diminished potency. Compounds were also evaluated in vitro against the parasites T. cruzi, T. brucei, and S. mansoni, revealing active compounds among this series. PMID:25712353

  3. Light-Induced Bistability in Iron(III) Spin-Transition Compounds of 5 X-Salicylaldehyde Thiosemicarbazone (X=H, Cl, Br).

    PubMed

    Yemeli, Eddy W T; Blake, Graeme R; Douvalis, Alexios P; Bakas, Thomas; Alberda van Ekenstein, Gert O R; van Koningsbruggen, Petra J

    2010-10-19

    The iron(III) spin-crossover compounds [Fe(Hthsa)(thsa)]⋅H2 O (1), [Fe(Hth5Clsa)(th5Clsa)2 ]⋅H2 O (2), and [Fe(Hth5Brsa)(th5Brsa)2 ]⋅H2 O (3) (H2 thsa=salicylaldehyde thiosemicarbazone, H2 th5Clsa=5-chlorosalicylaldehyde thiosemicarbazone, and H2 th5Brsa=5-bromosalicylaldehyde thiosemicarbazone) have been synthesized and their spin-transition properties investigated by magnetic susceptibility, Mössbauer spectroscopy, and differential scanning calorimetry measurements. The three compounds exhibit an abrupt spin transition with a thermal hysteresis effect. The more polarizable the substituent on the salicylaldehyde moiety, the more complete is the transition at room temperature with an increased degree of cooperativity. The molecular structures of 1 and 2 in the high-spin state are revealed. The occurrence of the light-induced excited-spin-state trapping phenomenon appears to be dependent on the substituent incorporated into the 5-position of the salicylaldehyde subunit. Whereas the compounds with an electron-withdrawing group (-Br or -Cl) exhibit light-induced trapped excited high-spin states with great longevity of metastability, the halogen-free compound does not, even though strong intermolecular interactions (such as hydrogen-bonding networks and π stacking) operate in the system. For compound 2, the surface level of photoconversion is less than 35 %. In contrast, compound 3 displays full photoexcitation.

  4. Copper(II)-Bis(Thiosemicarbazonato) Complexes as Antibacterial Agents: Insights into Their Mode of Action and Potential as Therapeutics

    PubMed Central

    Goytia, Maira M.; Donnelly, Paul S.; Shafer, William M.

    2015-01-01

    There is increasing interest in the use of lipophilic copper (Cu)-containing complexes to combat bacterial infections. In this work, we showed that Cu complexes with bis(thiosemicarbazone) ligands [Cu(btsc)] exert antibacterial activity against a range of medically significant pathogens. Previous work using Neisseria gonorrhoeae showed that Cu(btsc) complexes may act as inhibitors of respiratory dehydrogenases in the electron transport chain. We now show that these complexes are also toxic against pathogens that lack a respiratory chain. Respiration in Escherichia coli was slightly affected by Cu(btsc) complexes, but our results indicate that, in this model bacterium, the complexes act primarily as agents that deliver toxic Cu ions efficiently into the cytoplasm. Although the chemistry of Cu(btsc) complexes may dictate their mechanism of action, their efficacy depends heavily on bacterial physiology. This is linked to the ability of the target bacterium to tolerate Cu and, additionally, the susceptibility of the respiratory chain to direct inhibition by Cu(btsc) complexes. The physiology of N. gonorrhoeae, including multidrug-resistant strains, makes it highly susceptible to damage by Cu ions and Cu(btsc) complexes, highlighting the potential of Cu(btsc) complexes (and Cu-based therapeutics) as a promising treatment against this important bacterial pathogen. PMID:26239980

  5. Bis(2-chloroethoxy)methane

    Integrated Risk Information System (IRIS)

    Bis ( 2 - chloroethoxy ) methane ; CASRN 111 - 91 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for

  6. Bis(chloromethyl)ether (BCME)

    Integrated Risk Information System (IRIS)

    Bis ( chloromethyl ) ether ( BCME ) ; CASRN 542 - 88 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments f

  7. Bis(chloroethyl)ether (BCEE)

    Integrated Risk Information System (IRIS)

    Bis ( chloroethyl ) ether ( BCEE ) ; CASRN 111 - 44 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  8. 40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²- bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²- bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²- -1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene sulfonate); and ethanol, 2- oxy]ethoxy]...

  9. 40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²- bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²- bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²- -1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene sulfonate); and ethanol, 2- oxy]ethoxy]...

  10. 40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²- bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²- bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²- -1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene sulfonate); and ethanol, 2- oxy]ethoxy]...

  11. Copper(II) and nickel(II) complexes of benzyloxybenzaldehyde-4-phenyl-3-thiosemicarbazone: Synthesis, characterization and biological activity

    NASA Astrophysics Data System (ADS)

    Prathima, B.; Subba Rao, Y.; Adinarayana Reddy, S.; Reddy, Y. P.; Varada Reddy, A.

    2010-09-01

    Benzyloxybenzaldehyde-4-phenyl-3-thiosemicarbazone ligand (L) has been synthesized from benzyloxybenzaldehyde and 4-phenyl-3-thiosemicarbazide. Complexes of this ligand with chlorides of Cu(II) and Ni(II) have been prepared. The structure of the ligand (L) is proposed based on elemental analysis, IR and 1H NMR spectra. Its complexes with Cu(II) and Ni(II) ions are characterized from the studies of electronic as well as EPR spectra. On the basis of electronic and EPR studies, rhombically distorted octahedral structure has been proposed for Cu(II) complex while the Ni(II) complex has been found to acquire an octahedral structure. The ligand and their metal complexes have been tested in vitro for their biological effects. Their antibacterial activities against Gram-negative bacteria ( Escherichia coli and Klebsiella pneumoniae) and Gram-positive bacteria ( Staphylococcus aureus and Bacillus subtilis) have been investigated. The prepared metal complexes exhibit higher antibacterial activities than the parent ligand. The in vitro antioxidant activity of free ligand and its metal(II) complexes have also been investigated and the results however reveal that the ligand exhibits greater antioxidant activity than its complexes.

  12. Induction of Early Autophagic Process on Leishmania amazonensis by Synergistic Effect of Miltefosine and Innovative Semi-synthetic Thiosemicarbazone.

    PubMed

    Scariot, Débora B; Britta, Elizandra A; Moreira, Amanda L; Falzirolli, Hugo; Silva, Cleuza C; Ueda-Nakamura, Tânia; Dias-Filho, Benedito P; Nakamura, Celso V

    2017-01-01

    Drug combination therapy is a current trend to treat complex diseases. Many benefits are expected from this strategy, such as cytotoxicity decrease, retardation of resistant strains development, and activity increment. This study evaluated in vitro combination between an innovative thiosemicarbazone molecule - BZTS with miltefosine, a drug already consolidated in the leishmaniasis treatment, against Leishmania amazonensis. Cytotoxicity effects were also evaluated on macrophages and erythrocytes. Synergistic antileishmania effect and antagonist cytotoxicity were revealed from this combination therapy. Mechanisms of action assays were performed in order to investigate the main cell pathways induced by this treatment. Mitochondrial dysfunction generated a significant increase of reactive oxygen and nitrogen species production, causing severe cell injuries and promoting intense autophagy process and consequent apoptosis cell death. However, this phenomenon was not strong enough to promote dead in mammalian cell, providing the potential selective effect of the tested combination for the protozoa. Thus, the results confirmed that drugs involved in distinct metabolic routes are promising agents for drug combination therapy, promoting a synergistic effect.

  13. Synthesis, spectroscopic, anticancer and antibacterial studies of Ni(II) and Cu(II) complexes with 2-carboxybenzaldehyde thiosemicarbazone

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Vandana

    2014-08-01

    Ni(II) and Cu(II) complexes of 2-carboxybenzaldehyde thiosemicarbazone (L) were synthesized and investigated by their spectral and analytical data. These newly synthesized complexes have a composition of M(L)X(H2O)2 (where M = Ni(II), Cu(II) and X = Cl-, NO3-, CH3COO-) and (L) is the tridentate Schiff base ligand. The ligand and its complexes have been characterized on the basis of analytical, molar conductivity, magnetic susceptibility measurements, FT-IR, ESR, 1H NMR and electronic spectral analysis. All the compounds were non-electrolytic in nature. On the basis of spectral studies an octahedral geometry has been assigned for Ni(II) and a tetragonal geometry for Cu(II) complexes. The ligand and its metal complexes were screened for their anticancer studies against human breast cancer cell lines MCF-7 and calculated minimum inhibitory concentration and also for antibacterial activity using Kirby-Bauer single disk susceptibility test.

  14. Synthesis and evaluation of simple naked-eye colorimetric chemosensors for anions based on azo dye-thiosemicarbazones.

    PubMed

    Radchatawedchakoon, Widchaya; Sangsuwan, Withsakorn; Kruanetr, Senee; Sakee, Uthai

    2014-01-01

    A series of novel, highly selective azo dye-thiosemicarbazones based anion sensors (3e-f) have been synthesized from the condensation reaction between thiosemicarbazide and six different azo salicylaldehydes. The structure of the sensors was confirmed by spectroscopic methods. The selectivity and sensitivity in the recognition for acetate anion over other anions such as fluoride, chloride, iodide and dihydrogenphosphate anions were determined by naked-eyes and UV-vis spectra. The color of the solution containing sensor had an obvious change from light yellow to orange only after the addition of acetate anion in aqueous solution (water/dimethylsulfoxide, 7:3, v/v) while other anions did not cause obvious color change. The anion recognition property of the receptor via proton-transfer is monitored by UV-vis titration and (1)H NMR spectroscopy. Under condition in aqueous solution of sensor 3e (water/dimethylsulfoxide, 7:3, v/v), linearity range for the quantification of acetate anion was 1-22 μM and limit of detection (LOD) of acetate anion was 0.71 μM.

  15. Transition metal complexes of Vanillin- 4N-(2-pyridyl) thiosemicarbazone (H 2VPT); thermal, structural and spectroscopic studies

    NASA Astrophysics Data System (ADS)

    El-Reash, Gaber Abu; El-Ayaan, Usama; Gabr, I. M.; El-Rachawy, El-Bastawesy

    2010-04-01

    The present work carried out a study on the ligational behavior of the new ligand, Vanillin- 4N-(2-pyridyl) thiosemicarbazone (H 2VPT) 1 towards some transition metal ions namely, Mn 2+, Co 2+, Ni 2+, Cu 2+, Zn 2+,Cd 2+, Hg 2+ and U 6+. These complexes namely [Mn(HVPT)Cl] 2, [Co(VPT)(H 2O)] 2H 2O 3, [Ni(HVPT)Cl(H 2O)] 4, [Cu(HVPT)Cl(H 2O)] 5, [Zn(VPT)(H 2O)]H 2O 6, [Cd(HVPT)Cl(H 2O)] 7, [Hg(VPT)(H 2O)]H 2O 8 and [UO 2(H 2VPT)(OAc) 2]H 2O 9, were characterized by elemental analysis, spectral (IR, 1H NMR and UV-vis) and magnetic moment measurements. The suggested structures were confirmed by applying geometry optimization and conformational analysis. Thermal properties and decomposition kinetics of all compounds are investigated. The interpretation, mathematical analysis and evaluation of kinetic parameters ( E, A, Δ H, Δ S and Δ G) of all thermal decomposition stages have been evaluated using Coats-Redfern equation. ESR spectra of [Cu(HVPT)Cl]H 2O at room temperature show broad signal, indicating spin-exchange interactions between copper(II) ions.

  16. Induction of Early Autophagic Process on Leishmania amazonensis by Synergistic Effect of Miltefosine and Innovative Semi-synthetic Thiosemicarbazone

    PubMed Central

    Scariot, Débora B.; Britta, Elizandra A.; Moreira, Amanda L.; Falzirolli, Hugo; Silva, Cleuza C.; Ueda-Nakamura, Tânia; Dias-Filho, Benedito P.; Nakamura, Celso V.

    2017-01-01

    Drug combination therapy is a current trend to treat complex diseases. Many benefits are expected from this strategy, such as cytotoxicity decrease, retardation of resistant strains development, and activity increment. This study evaluated in vitro combination between an innovative thiosemicarbazone molecule – BZTS with miltefosine, a drug already consolidated in the leishmaniasis treatment, against Leishmania amazonensis. Cytotoxicity effects were also evaluated on macrophages and erythrocytes. Synergistic antileishmania effect and antagonist cytotoxicity were revealed from this combination therapy. Mechanisms of action assays were performed in order to investigate the main cell pathways induced by this treatment. Mitochondrial dysfunction generated a significant increase of reactive oxygen and nitrogen species production, causing severe cell injuries and promoting intense autophagy process and consequent apoptosis cell death. However, this phenomenon was not strong enough to promote dead in mammalian cell, providing the potential selective effect of the tested combination for the protozoa. Thus, the results confirmed that drugs involved in distinct metabolic routes are promising agents for drug combination therapy, promoting a synergistic effect. PMID:28270805

  17. A study on the alkaline hydrolysis of isatin-β-thiosemicarbazone by capillary electrophoresis with enhanced sample loadability.

    PubMed

    Kruk, Pavol; Stankovičová, Henrieta; Bodor, Róbert; Gáplovský, Anton; Masár, Marián

    2012-05-11

    An analytical potential of capillary zone electrophoresis (CZE) with enhanced sample loadability (a 200nL injection volume) in determination of alkaline hydrolysis products of isatin-β-thiosemicarbazone (IBT), a compound with important biological activity, has been studied. The CZE separation conditions for a complete resolution of transformation products, i.e. 2-aminophenylglyoxalate, 2-(2-aminophenyl)-2-semicarbazonoethane, anthranilate and E-Z geometric isomers of 2-(2-aminophenyl)-2-thiosemicarbazonoethane, have been optimized. CZE separations with UV detection at 240 nm were performed using glycine running buffer at high pH (9.2) and containing an uncharged β-cyclodextrin as a complexing agent. High sensitivity (with detection limits ranging from 0.1 to 1.2 μM), good repeatability (RSD of migration times less than 0.4% and 0.4-3.4% RSD of peak areas) and linearity over two orders of magnitude were achieved for the compounds studied. The employed CZE method, characterized by simple sample handling (only dilution step needed) and total analysis time of less than 15 min, has been applied successfully to time monitoring of the transformation of IBT in alkaline media. Under optimized CZE conditions, the effect of pH of reaction media, implemented by different concentration of NaOH (0.1-100mM), on the course of the alkaline hydrolysis of IBT was studied in this respect, as well.

  18. Synthesis and evaluation of simple naked-eye colorimetric chemosensors for anions based on azo dye-thiosemicarbazones

    NASA Astrophysics Data System (ADS)

    Radchatawedchakoon, Widchaya; Sangsuwan, Withsakorn; Kruanetr, Senee; Sakee, Uthai

    2014-03-01

    A series of novel, highly selective azo dye-thiosemicarbazones based anion sensors (3e-f) have been synthesized from the condensation reaction between thiosemicarbazide and six different azo salicylaldehydes. The structure of the sensors was confirmed by spectroscopic methods. The selectivity and sensitivity in the recognition for acetate anion over other anions such as fluoride, chloride, iodide and dihydrogenphosphate anions were determined by naked-eyes and UV-vis spectra. The color of the solution containing sensor had an obvious change from light yellow to orange only after the addition of acetate anion in aqueous solution (water/dimethylsulfoxide, 7:3, v/v) while other anions did not cause obvious color change. The anion recognition property of the receptor via proton-transfer is monitored by UV-vis titration and 1H NMR spectroscopy. Under condition in aqueous solution of sensor 3e (water/dimethylsulfoxide, 7:3, v/v), linearity range for the quantification of acetate anion was 1-22 μM and limit of detection (LOD) of acetate anion was 0.71 μM.

  19. Copper(II) and nickel(II) complexes of benzyloxybenzaldehyde-4-phenyl-3-thiosemicarbazone: Synthesis, characterization and biological activity.

    PubMed

    Prathima, B; Subba Rao, Y; Adinarayana Reddy, S; Reddy, Y P; Varada Reddy, A

    2010-09-15

    Benzyloxybenzaldehyde-4-phenyl-3-thiosemicarbazone ligand (L) has been synthesized from benzyloxybenzaldehyde and 4-phenyl-3-thiosemicarbazide. Complexes of this ligand with chlorides of Cu(II) and Ni(II) have been prepared. The structure of the ligand (L) is proposed based on elemental analysis, IR and (1)H NMR spectra. Its complexes with Cu(II) and Ni(II) ions are characterized from the studies of electronic as well as EPR spectra. On the basis of electronic and EPR studies, rhombically distorted octahedral structure has been proposed for Cu(II) complex while the Ni(II) complex has been found to acquire an octahedral structure. The ligand and their metal complexes have been tested in vitro for their biological effects. Their antibacterial activities against Gram-negative bacteria (Escherichia coli and Klebsiella pneumoniae) and Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis) have been investigated. The prepared metal complexes exhibit higher antibacterial activities than the parent ligand. The in vitro antioxidant activity of free ligand and its metal(II) complexes have also been investigated and the results however reveal that the ligand exhibits greater antioxidant activity than its complexes.

  20. Synthesis and evaluation of isatin-β-thiosemicarbazones as novel agents against antibiotic-resistant Gram-positive bacterial species.

    PubMed

    Zhang, Xu-Meng; Guo, Hui; Li, Zai-Shun; Song, Fu-Hang; Wang, Wei-Min; Dai, Huan-Qin; Zhang, Li-Xin; Wang, Jian-Guo

    2015-08-28

    Methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin-resistant Enterococcus (VRE) have caused an increasing mortality rate, which means that antibiotic resistance is becoming an important health issue. In the course to screen new agents for resistant bacteria, we identified that a series of isatin-β-thiosemicarbazones (IBTs) could inhibit the growth of MRSA and VRE. This was the first time that the "familiar" IBT compounds exhibited significant anti Gram-positive pathogen activity. Against a clinical isolated MRSA strain, 20 of the 51 synthesized compounds showed minimum inhibitory concentration (MIC) data of 0.78 mg/L and another 12 novel compounds had MICs of 0.39 mg/L. Moreover, these compounds also inhibited Enterococcus faecalis and VRE at similar levels, indicating that IBTs might have different mode of action compared with vancomycin. For these IBTs, comparative field analysis (CoMFA) models were further established to understand the structure-activity relationships in order to design new compounds from steric and electrostatic contributions. This work has suggested that IBTs can be considered as potential lead compounds to discover antibacterial inhibitors to combat drug resistance.

  1. Novel and potent anti-tumor and anti-metastatic di-2-pyridylketone thiosemicarbazones demonstrate marked differences in pharmacology between the first and second generation lead agents

    PubMed Central

    Sestak, Vit; Stariat, Jan; Cermanova, Jolana; Potuckova, Eliska; Chladek, Jaroslav; Roh, Jaroslav; Bures, Jan; Jansova, Hana; Prusa, Petr; Sterba, Martin; Micuda, Stanislav; Simunek, Tomas; Kalinowski, Danuta S.; Richardson, Des R.; Kovarikova, Petra

    2015-01-01

    Di(2-pyridyl)ketone 4,4-dimethyl-3-thiosemicarbazone (Dp44mT) and di(2-pyridyl)ketone 4-cyclohexyl-4-methyl-3-thiosemicarbazone (DpC) are novel, highly potent and selective anti-tumor and anti-metastatic drugs. Despite their structural similarity, these agents differ in their efficacy and toxicity in-vivo. Considering this, a comparison of their pharmacokinetic and pharmaco/toxico-dynamic properties was conducted to reveal if these factors are involved in their differential activity. Both compounds were administered to Wistar rats intravenously (2 mg/kg) and their metabolism and disposition were studied using UHPLC-MS/MS. The cytotoxicity of both thiosemicarbazones and their metabolites was also examined using MCF-7, HL-60 and HCT116 tumor cells and 3T3 fibroblasts and H9c2 cardiac myoblasts. Their intracellular iron-binding ability was characterized by the Calcein-AM assay and their iron mobilization efficacy was evaluated. In contrast to DpC, Dp44mT undergoes rapid demethylation in-vivo, which may be related to its markedly faster elimination (T1/2 = 1.7 h for Dp44mT vs. 10.7 h for DpC) and lower exposure. Incubation of these compounds with cancer cells or cardiac myoblasts did not result in any significant metabolism in-vitro. The metabolism of Dp44mT in-vivo resulted in decreased anti-cancer activity and toxicity. In conclusion, marked differences in the pharmacology of Dp44mT and DpC were observed and highlight the favorable pharmacokinetics of DpC for cancer treatment. PMID:26623727

  2. Synthesis and characterization of mixed-ligand diimine-piperonal thiosemicarbazone complexes of ruthenium(II): Biophysical investigations and biological evaluation as anticancer and antibacterial agents

    PubMed Central

    Beckford, Floyd A.; Thessing, Jeffrey; Shaloski, Michael; Mbarushimana, P. Canisius; Brock, Alyssa; Didion, Jacob; Woods, Jason; Gonzalez-Sarrías, Antonio; Seeram, Navindra P.

    2011-01-01

    We have used a novel microwave-assisted method developed in our laboratories to synthesize a series of ruthenium-thiosemicarbazone complexes. The new thiosemicarbazone ligands are derived from benzo[d][1,3]dioxole-5-carbaldehyde (piperonal) and the complexes are formulated as [(diimine)2Ru(TSC)](PF6)2 (where the TSC is the bidentate thiosemicarbazone ligand). The diimine in the complexes is either 2,2'-bipyridine or 1,10-phenanthroline. The complexes have been characterized by spectroscopic means (NMR, IR and UV-Vis) as well as by elemental analysis. We have studied the biophysical characteristics of the complexes by investigating their anti-oxidant ability as well as their ability to disrupt the function of the human topoisomerase II enzyme. The complexes are moderately strong binders of DNA with binding constants of 104 M−1. They are also strong binders of human serum albumin having binding constants on the order of 104 M−1. The complexes show good in vitro anticancer activity against human colon cancer cells, Caco-2 and HCT-116 and indeed show some cytotoxic selectivity for cancer cells. The IC50 values range from 7 – 159 μM (after 72 h drug incubation). They also have antibacterial activity against Gram-positive strains of pathogenic bacteria with IC50 values as low as 10 μM; little activity was seen against Gram-negative strains. It has been established that all the compounds are catalytic inhibitors of human topoisomerase II. PMID:21552381

  3. Metal-catalysed oxidation processes in thiosemicarbazones: new complexes with the ligand N-{2-([4-N-ethylthiosemicarbazone]methyl)phenyl}-p-toluenesulfonamide.

    PubMed

    Pedrido, Rosa; Romero, María J; Bermejo, Manuel R; González-Noya, Ana M; García-Lema, Iria; Zaragoza, Guillermo

    2008-01-01

    The coordination behaviour of a new thiosemicarbazone Schiff-base building block, N-{2-([4-N-ethylthiosemicarbazone]methyl)phenyl}-p-toluenesulfonamide, H2L1 (1), incorporating a bulky tosyl group, towards Mn II, Fe II, Co II, Ni II, Cu II, Zn II, Cd II, Ag I, Sn II, and Pb II has been investigated by means of an electrochemical preparative procedure. Most metal complexes of L1 have the general formula [M(L1)]2.nX (M=Mn, Fe, Co, Ni, Cu, Cd, Pb; n=0-4, X=H2O or CH3CN), as confirmed by the structure of [Pb(L1)]2 (15), in which the lone pair on lead is stereochemically active. This lead(II) complex shows an intense fluorescence emission with a quantum yield of 0.13. In the case of silver, the complex formed was found to possess a stoichiometry of [Ag2(L1)]2.3H2O. During reactions with manganese and copper metals, interesting catalysed processes have been found to take place, with remarkable consequences regarding the ligand skeleton structure. In synthesising the manganese complex, we obtained an unexpected dithiolate thiosemicarbazone tosyl ligand, H2L2, as a side-product, which has been fully characterised, including by X-ray diffraction analysis. In the case of copper, the solid complex has the formula [CuL1]2, but the crystallised product shows the copper atoms coordinated to a new cyclised thiosemicarbazone ligand, H2L3, as in the structures of the complexes [Cu(L3)]2.CH3CN (8) and [Cu(L3)(H2O)]2.CH3CN.H2O (9). The zinc complex [Zn(L1)]4 (12) displays a particular tetranuclear zeolite-type structure capable of hosting small molecules or ions, presumably through hydrogen bonding.

  4. A 119Sn Mössbauer Study of Tin(IV) Complexes of 2- and 4-Benzoylpyridine Thiosemicarbazone and 4-Benzoylpyridine Semicarbazone

    NASA Astrophysics Data System (ADS)

    Pérez-Rebolledo, Anayive; Ardisson, José D.; de Lima, Geraldo M.; Macedo, Waldemar A. A.; Beraldo, Heloisa

    2005-06-01

    A 119Sn Mössbauer study was carried out of tin(IV) complexes with 2-benzoylpyridine thiosemicarbazone (H2Bz4DH) and its N(4)-methyl (H2Bz4M) and N(4)-phenyl (H2Bz4Ph) derivatives: [Sn(2Bz4DH)Cl3] (1), [Sn(2Bz4DH)PhCl2] (2), [Sn(2Bz4M)Cl3] (3), [H22Bz4M]2[Ph2SnCl4] (4), [Sn(2Bz4Ph)PhCl2] (5), [Sn(2Bz4Ph)Ph2Cl] (6), in which H2Bz4R stands for the neutral ligand and 2Bz4R stands for the anionic thiosemicarbazone. In addition, 119Sn Mössbauer studies of the tin(IV) complexes [Sn(H4Bz4DH)2Cl4H2O] (7), [Sn(H4BzPS)2Cl4H2O] (8) with 4-benzoylpyridine thiosemicarbazone (H4Bz4DH) and the correspondent semicarbazone (H4BzPS) were performed. The isomer shifts decrease upon coordination due to the variation in the percentage of s character as tin changes from approximately sp3 hybridization in the tin salts to sp3d2 in the octahedral or sp3d3 in the heptahedral complexes. The Mössbauer parameters of compound (4) showed the existence of two tin(IV) sites, which have been attributed to the presence of the cis and trans isomers.

  5. L- and D-proline thiosemicarbazone conjugates: coordination behavior in solution and the effect of copper(II) coordination on their antiproliferative activity.

    PubMed

    Milunovic, Miljan N M; Enyedy, Éva A; Nagy, Nóra V; Kiss, Tamás; Trondl, Robert; Jakupec, Michael A; Keppler, Bernhard K; Krachler, Regina; Novitchi, Ghenadie; Arion, Vladimir B

    2012-09-03

    Two enantiomerically pure thiosemicarbazone-proline conjugates with enhanced aqueous solubility, namely, 2-hydroxy-3-methyl-(S)-pyrrolidine-2-carboxylate-5-methylbenzaldehyde thiosemicarbazone [L-Pro-STSC or (S)-H(2)L] and 2-hydroxy-3-methyl-(R)-pyrrolidine-2-carboxylate-5-methylbenzaldehyde thiosemicarbazone [D-Pro-STSC or (R)-H(2)L] have been synthesized and characterized by elemental analysis, spectroscopic methods (UV-vis and (1)H and (13)C NMR), and electrospray ionization mass spectrometry. The metal complexation behavior of L-Pro-STSC, stoichiometry, and thermodynamic stability of iron(II), iron(III), copper(II), and zinc(II) complexes in 30% (w/w) dimethyl sulfoxide/H(2)O solvent mixture have been studied by pH-potentiometric, UV-vis-spectrophotometric, circular dichroism, electron paramagnetic resonance, (1)H NMR spectroscopic, and spectrofluorimetric measurements. By the reaction of CuCl(2)·2H(2)O with (S)-H(2)L and (R)-H(2)L, respectively, the complexes [Cu[(S)-H(2)L]Cl]Cl and [Cu[(R)-H(2)L]Cl]Cl have been prepared and comprehensively characterized. An X-ray diffraction study of [Cu[(R)-H(2)L]Cl]Cl showed the formation of a square-planar copper(II) complex, which builds up stacks with interplanar separation of 3.3 Å. The antiproliferative activity of two chiral ligands and their corresponding copper(II) complexes has been tested in two human cancer cell lines, namely, SW480 (colon carcinoma) and CH1 (ovarian carcinoma). The thiosemicarbazone-proline conjugates L- and D-Pro-STSC show only moderate cytotoxic potency with IC(50) values of 62 and 75 μM, respectively, in CH1 cells and >100 μM in SW480 cells. However, the corresponding copper(II) complexes are 13 and 5 times more potent in CH1 cells, based on a comparison of IC(50) values, and in SW480 cells the increase in the antiproliferative activity is even higher. In both tested cell lines, L-Pro-STSC as well as its copper(II) complex show slightly stronger antiproliferative activity than the

  6. Bis(adeninium) bis­(hydrogensulfate) sulfate

    PubMed Central

    Guenifa, Fatiha; Bendjeddou, Lamia; Cherouana, Aouatef; Dahaoui, Slimane; Lecomte, Claude

    2012-01-01

    The title compound, 2C5H7N5 2+·2HSO4 −·SO4 2−, was synthesized from adenine and sulfuric acid. The asymmetric unit contains two diprotonated adeninium cations, two bis­ulfate anions and one sulfate anion. The crystal structure is stabilized by classical N—H⋯O and O—H⋯O hydrogen bonds, and weak C—H⋯O and C—H⋯N hydrogen bonds, generating a three-dimensional network. PMID:23468782

  7. Metal-induced cyclization of thiosemicarbazones derived from beta-keto amides and beta-keto esters: open-chain and cyclized ligands in zinc(II) complexes.

    PubMed

    Casas, José S; Castaño, María V; Castellano, Eduardo E; Ellena, Javier; García-Tasende, María S; Gato, Angeles; Sánchez, Agustín; Sanjuán, Luisa M; Sordo, José

    2002-03-25

    The reactions of Zn(OAc)(2) with acetoacetanilide, methyl acetoacetate, o-acetoacetanisidide, and ethyl 2-methylacetoacetate thiosemicarbazones (HTSC(1), HTSC(2), HTSC(3), and HTSC(4), respectively) were explored in methanol. With HTSC(1), HTSC(2), and HTSC(3), following isolation of the corresponding zinc(II) thiosemicarbazonates [Zn(TSC(x))(2)] (x = 1, 2, 3), the mother liquors afforded pyrazolonate complexes [ZnL(1)(2)(H(2)O)] (HL(1) = 2,5-dihydro-3-methyl-5-oxo-1H-pyrazole-1-carbothioamide) that had been formed by cyclization of the corresponding TSC(-). The reaction of HTSC(4) with zinc(II) acetate gave only the pyrazolonate complex [ZnL(2)(2)(H(2)O)] (HL(2) = 2,5-dihydro-3,4-dimethyl-5-oxo-1H-pyrazole-1-carbothioamide). All compounds were studied by IR and NMR spectroscopy, and HTSC(3), [Zn(TSC(3))(2)] x DMSO, [ZnL(1)(2)(H(2)O)] x 2DMSO, and [ZnL(2)(2)(H(2)O)] x 2DMSO were also studied by X-ray diffractometry, giving a thorough picture of the cyclization process. In preliminary tests of the effects of HL(1) and [ZnL(1)(2)(H(2)O)] on rat paw inflammatory edema induced by carrageenan, HL(1) showed antiinflammatory activity.

  8. Evaluation of anti-inflammatory effect of derivative (E)-N-(4-bromophenyl)-2-(thiophen-2-ylmethylene)-thiosemicarbazone.

    PubMed

    de Oliveira, Jamerson Ferreira; Nonato, Fabiana Regina; Zafred, Rafael Rosolen Teixeira; Leite, Nayara Maria Siqueira; Ruiz, Ana Lúcia Tasca Gois; de Carvalho, João Ernesto; da Silva, Anekécia Lauro; de Moura, Ricardo Olímpio; Alves de Lima, Maria do Carmo

    2016-05-01

    The present study aimed to further investigate the anti-inflammatory activity of (E)-N-(4-bromophenyl)-2-(thiophen-2-ylmethylene)-thiosemicarbazone (BTTSC) as well as its antinociceptive effects. The anti-inflammatory activity was assessed using the model of ear edema induced by croton oil-induced and also evaluated in models of paw edema carrageenan-induced and by compound 48/80. Evaluation of the antinociceptive effect was performed through formalin test. In the nociception test induced by formalin the BTTSC showed activity in both phases of the pain, highlighting inflammatory pain, where it was able to reduce the time to paw lick 62.3, 84.30 and 100% at doses of 30, 100 and 300mgkg(-1). The anti-inflammatory activity was performed ear edema induced by croton oil, where none of the doses tested was capable of significantly regress edema. The paw edema carrageenan-induced showed activity compound, where the edema was reduced by 81.9 and 83.2% in the first two times of the experiment at the highest dose used. The paw edema assay induced by compound 48/80, showed that BTTSC after 15min of the inoculum phlogistic agent showed significant reduction of edema with values of 56.53% at a dose of 30mgkg(-1). Our results suggesting this compound exerts its antinociception effects connected with peripheral mechanisms. Furthermore, the compound was able to act in two phases of inflammation carrageenan-induced, highlighting the initial phase. This suggests an action on the early mediators of inflammation. The paw edema assay induced by compound 48/80 confirmed our hypothesis indicating action of the compound via histamine.

  9. Characterization of the anticancer effects of S115, a novel heteroaromatic thiosemicarbazone compound, in vitro and in vivo

    PubMed Central

    Liu, Min-yu; Xiao, Lin; Dong, Yu-qiong; Liu, Ying; Cai, Li; Xiong, Wei-xia; Yao, Yu-long; Yin, Ming; Liu, Quan-hai

    2014-01-01

    Aim: To investigate the anticancer effects of S115, a novel heteroaromatic thiosemicarbazone compound in vitro and in vivo. Methods: The anti-proliferative action of S115 was analyzed in 12 human and mouse cancer cell lines using MTT assay. Autograft and xenograft cancer models were made by subcutaneous inoculation of cancer cells into mice or nude mice. The mice were orally treated with S115 (2, 8, 32 mg·kg−1·d−1) for 7 d, and the tumor size was measured every 3 d. Cell apoptosis and cell cycle distribution were examined using flow cytometry, gene expression profile analyses, Western blots and RT-PCR. Results: The IC50 values of S115 against 12 human and mouse cancer cell lines ranged from 0.3 to 6.6 μmol/L. The tumor growth inhibition rate caused by oral administration of S115 (32 mg·kg−1·d−1) were 89.7%, 81.7%, 78.4% and 77.8%, respectively, in mouse model of B16 melanoma, mouse model of Colon26 colon cancer, nude mouse model of A549 lung cancer and nude mouse model of SK-OV-3 ovarian cancer. Furthermore, oral administration of S115 (7.5 mg·kg−1·d−1) synergistically enhanced the anticancer effects of cyclophosphamide, cisplatin, or 5-fluorouracil in mouse model of S180 sarcoma. Treatment of A549 human lung cancer cells with S115 (1.5 μmol/L) induced G0/G1 cell cycle arrest, and increased apoptosis. Furthermore, S115 downregulated the level of ubiquitin, and upregulated the level of Tob2 in A549 cells. Conclusion: S115 exerts anticancer effects against a variety of cancer cells in vitro and in grafted cancer models by inducing apoptosis, downregulating ubiquitin and upregulating Tob2. PMID:25220642

  10. Nickel(II) Complex of Polyhydroxybenzaldehyde N4-Thiosemicarbazone Exhibits Anti-Inflammatory Activity by Inhibiting NF-κB Transactivation

    PubMed Central

    Loh, Sheng Wei; Looi, Chung Yeng; Hassandarvish, Pouya; Phan, Alicia Yi Ling; Wong, Won Fen; Wang, Hao; Paterson, Ian C.; Ea, Chee Kwee; Mustafa, Mohd Rais; Maah, Mohd Jamil

    2014-01-01

    Background The biological properties of thiosemicarbazone have been widely reported. The incorporation of some transition metals such as Fe, Ni and Cu to thiosemicarbazone complexes is known to enhance its biological effects. In this study, we incorporated nickel(II) ions into thiosemicarbazone with N4-substitution groups H3L (H; H3L1, CH3; H3L2, C6H5; H3L3 and C2H5; H3L4) and examined its potential anti-inflammatory activity. Methodology/Principal Findings Four ligands (1–4) and their respective nickel-containing complexes (5–8) were synthesized and characterized. The compounds synthesized were tested for their effects on NF-κB nuclear translocation, pro-inflammatory cytokines secretion and NF-κB transactivation activity. The active compound was further evaluated on its ability to suppress carrageenan-induced acute inflammation in vivo. A potential binding target of the active compound was also predicted by molecular docking analysis. Conclusions/Significance Among all synthesized compounds tested, we found that complex [Ni(H2L1)(PPh3)]Cl (5) (complex 5), potently inhibited IκBα degradation and NF-κB p65 nuclear translocation in LPS-stimulated RAW264.7 cells as well as TNFα-stimulated HeLa S3 cells. In addition, complex 5 significantly down-regulated LPS- or TNFα-induced transcription of NF-κB target genes, including genes that encode the pro-inflammatory cytokines TNFα, IFNβ and IL6. Luciferase reporter assays confirmed that complex 5 inhibited the transactivation activity of NF-κB. Furthermore, the anti-inflammatory effect of complex 5 was also supported by its suppressive effect on carrageenan-induced paw edema formation in wild type C57BL/6 mice. Interestingly, molecular docking study showed that complex 5 potentially interact with the active site of IKKβ. Taken together, we suggest complex 5 as a novel NF-κB inhibitor with potent anti-inflammatory effects. PMID:24977407

  11. Bis(o-trifluoromethylphenyl)dithiophosphinic Methyl Ester

    SciTech Connect

    John R. Klaehn; Dean R. Peterman; Mason K. Harrup; Thomas A. Luther; Lee M. Daniels

    2011-05-01

    When bis(o-trifluoromethylphenyl)dithiophosphinic acid (1) was dissolved in methanol, crystals of bis(o-trifluoromethylphenyl)dithiophosphinic methyl ester (2) were isolated. The structure of dithiophosphinic methyl ester (2) has been identified via single-crystal X-ray diffraction and multinuclear NMR studies. Compound 2 is remarkable in that the dithiophosphinic (PS2) core is preserved during this transformation. Many dithiophosphinic acids degrade to other compounds over time which results in formation of dithiophosphinic dimers, like the bis(dithiophosphinic) anhydride. The transformation to 2 suggests that the o-trifluoromethylphenyl groups on phosphorus assist in retaining the PS2 core, possibly by steric hindrance.

  12. Molecular interactions in bis(2-aminopyridinium) malonate: A crystal isostructural to bis(2-aminopyridinium) maleate crystal

    NASA Astrophysics Data System (ADS)

    Chitra, R.; Choudhury, R. R.; Thiruvenkatam, Vijay; Hosur, M. V.; Guru Row, T. N.

    2012-02-01

    Crystals of a new salt in 2:1 ratio of 2-aminopyridine and malonic acid are grown by slow evaporation. These crystals of bis(2-aminopyridinium) malonate are orthorhombic and belong to the non-centrosymmetric space group, Fdd2 with parameters a = 22.0786(6), b = 23.0218(6), c = 5.5595(1) Å and Z = 8 at 300 K. The crystals are isostructural to those of bis(2-aminopyridinium) maleate, which is a NLO material. The isostructurality index between bis(2-aminopyridinium) maleate and bis(2-aminopyridinium) malonate was also calculated. The hyperpolarizability calculated using semi empirical method MOPAC2009 showed that bis(2-aminopyridinium) malonate has slightly higher β value compared to that of bis(2-aminopyridinium) maleate.

  13. A hexadentate bis(thiosemicarbazonato) ligand: rhenium(V), iron(III) and cobalt(III) complexes.

    PubMed

    Paterson, Brett M; White, Jonathan M; Donnelly, Paul S

    2010-03-21

    A new 1,3-diaminopropane bridged bis(thiosemicarbazone) ligand (H(4)L) has been synthesised. The new hexadentate ligand is capable of forming six coordinate complexes with rhenium(V), iron(III) and cobalt(III). In the case of the iron(III) and cobalt(III) complexes the ligand doubly deprotonates to give the monocations [Fe(III)(H(2)L)](+) and [Co(III)(H(2)L)](+) in which the metal ion is in a distorted octahedral environment. In the rhenium(V) complex the ligand loses four protons by deprotonation of both secondary amine nitrogen atoms to give [Re(V)(L)](+) with the metal ion in a distorted trigonal prismatic coordination environment. [Re(V)(L)](+) represents a rare example of a rhenium(V) complex that does not contain one of the ReO(3+), ReN(2+) or Re(NPh)(2+) cores. The new ligand and metal complexes have been characterised by a combination of NMR spectroscopy, X-ray crystallography, mass spectrometry and microanalysis. The electrochemistry of [Fe(III)(H(2)L)](+), [Co(III)(H(2)L)](+) and [Re(V)(L)](+) has been investigated by cyclic voltammetry with each complex undergoing a single electron reduction event. It is possible to prepare the rhenium(V) complex from ReOCl(3)(PPh(3))(2) or directly from [ReO(4)](-) with the addition of a reductant, which suggests the new ligand may be of interest in the development of rhenium radiopharmaceuticals.

  14. Spectral studies on Co(II), Ni(II) and Cu(II) complexes with thiosemicarbazone (L1) and semicarbazone (L2) derived from 2-acetyl furan.

    PubMed

    Chandra, Sulekh; Kumar, Anil

    2007-04-01

    Co(II), Ni(II) and Cu(II) complexes are synthesized with thiosemicarbazone (L1) and semicarbazone (L2) derived from 2-acetyl furan. These complexes are characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, electronic and EPR spectral studies. The molar conductance measurements of the complexes in DMSO correspond to non-electrolytic nature except Ni(L)2(NO3)2, which is 1:2 electrolyte. All the complexes are of high-spin type. On the basis of spectral studies an octahedral geometry may be assigned for Co(II) and Ni(II) complexes except nitrato complexes of Ni(II) which is of tetrahedral geometry, whereas tetragonal geometry for Cu(II) complexes.

  15. Spectral, IR and magnetic studies of Mn(II), Co(II), Ni(II) and Cu(II) complexes with pyrrole-2-carboxyaldehyde thiosemicarbazone (L).

    PubMed

    Chandra, Sulekh; Kumar, Anil

    2007-11-01

    Mn(II), Co(II), Ni(II) and Cu(II) complexes are synthesized with thiosemicarbazone (L) derived from pyrrole-2-carboxyaldehyde. These complexes are characterized by elemental analysis, molar conductance, magnetic susceptibility measurement, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO indicates that the complexes are non-electrolyte except Co(L)2(NO3)2 and Ni(L)2(NO3)2 complexes which are 1:2 electrolyte. All the complexes are of high-spin type. On the basis of spectral studies an octahedral geometry may be assigned for Mn(II), Co(II) and Ni(II) complexes except Co(L)2(NO3)2 and Ni(L)2(NO3)2 which are of tetrahedral geometry. A tetragonal geometry may be suggested for Cu(II) complexes.

  16. Influence of terminal substitution on structural, DNA, protein binding, anticancer and antibacterial activities of palladium(II) complexes containing 3-methoxy salicylaldehyde-4(N) substituted thiosemicarbazones.

    PubMed

    Kalaivani, P; Prabhakaran, R; Ramachandran, E; Dallemer, F; Paramaguru, G; Renganathan, R; Poornima, P; Vijaya Padma, V; Natarajan, K

    2012-02-28

    The variable chelating behavior of 3-methoxysalicylaldehyde-4(N)-substituted thiosemicarbazones was observed in equimolar reactions with [PdCl(2)(PPh(3))(2)]. The new complexes were characterized by various analytical, spectroscopic techniques (mass, (1)H-NMR, absorption, IR). All the new complexes were structurally characterized by single crystal X-ray diffraction. Crystallographic results showed that the ligands H(2)L(1) and H(2)L(4) are coordinated as binegative tridentate ONS donor ligands in the complexes 1 and 4 by forming six and five member rings. However, the ligands H(2)L(2) and H(2)L(3) bound to palladium in 2 and 3 as uninegative bidentate NS donors by forming a five member chelate ring. From this study, it was found that the substitution on terminal 4(N)-nitrogen may have an influence on the chelating ability of thiosemicarbazone. The presence of hydrogen bonding in 2 and 3 might be responsible for preventing the coordination of phenolic oxygen to the metal ion. The interaction of the complexes with calf-thymus DNA (CT-DNA) has been explored by absorption and emission titration methods. Based on the observations, an electrostatic binding mode of DNA has been proposed. The protein binding studies were monitored by quenching of tryptophan and tyrosine residues in the presence of complexes using Lysozyme as model protein. Antibacterial activity studies of the complexes have been screened against pathogenic bacteria such as Enterococcus faecalis, Staphylococcus aureus, Escherichia coli, Klebsiella pneumonia and Pseudomonas aeruginosa. MIC50 values of the complexes showed that they exhibited significant activity against the pathogens and among them, 3 exhibited higher activity. Further, anticancer activity of the complexes on the lung cancer cell line A549 has also been studied.

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

    PubMed

    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.

  18. QSAR of anticancer compounds. Bis(11-oxo-11H-indeno[1,2-b]quinoline-6-carboxamides), bis(phenazine-1-carboxamides), and bis(naphthalimides).

    PubMed

    Mekapati, S B; Denny, W A; Kurup, A; Hansch, C

    2001-11-01

    QSAR have been developed for the anticancer activity (growth inhibition) of various tumor cells by bis(11-oxo-11H-indeno[1,2-b]quinoline-6-carboxamides), bis(phenazine-1-carboxamides), and bis(naphthalimides). Of the seven QSAR, positive hydrophobic interactions are found in only two examples: bis(naphthalimides) versus human colon cancer cells. This is consistent with other QSAR of anticancer compounds where hydrophobic interactions are found to be unimportant.

  19. Briefwechsel uber die Partikel "bis" (An Exchange of Letters about the Particle "bis").

    ERIC Educational Resources Information Center

    Ludwig, Horst; Holschuh, Albrecht

    1990-01-01

    A discussion, in the form of an animated letter exchange, argues that, contrary to most current grammatical descriptions, the German particle "bis" should not be viewed as a preposition governing the accusative case. Rather, it is demonstrated that "bis" most often occurs as a proclitic adverb. (16 references) (JTC)

  20. 40 CFR 721.1187 - Bis(imidoethylene) benzene.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Bis(imidoethylene) benzene. 721.1187... Substances § 721.1187 Bis(imidoethylene) benzene. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance bis(imidoethylene)benzene (PMN P-93-1447) is subject to...

  1. 40 CFR 721.1187 - Bis(imidoethylene) benzene.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Bis(imidoethylene) benzene. 721.1187... Substances § 721.1187 Bis(imidoethylene) benzene. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance bis(imidoethylene)benzene (PMN P-93-1447) is subject to...

  2. 40 CFR 721.1187 - Bis(imidoethylene) benzene.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Bis(imidoethylene) benzene. 721.1187... Substances § 721.1187 Bis(imidoethylene) benzene. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance bis(imidoethylene)benzene (PMN P-93-1447) is subject to...

  3. 40 CFR 721.1187 - Bis(imidoethylene) benzene.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Bis(imidoethylene) benzene. 721.1187... Substances § 721.1187 Bis(imidoethylene) benzene. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance bis(imidoethylene)benzene (PMN P-93-1447) is subject to...

  4. 40 CFR 721.1187 - Bis(imidoethylene) benzene.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Bis(imidoethylene) benzene. 721.1187... Substances § 721.1187 Bis(imidoethylene) benzene. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance bis(imidoethylene)benzene (PMN P-93-1447) is subject to...

  5. 40 CFR 721.10714 - Zinc bis(dialkyldithiocarbamate) (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Zinc bis(dialkyldithiocarbamate... Specific Chemical Substances § 721.10714 Zinc bis(dialkyldithiocarbamate) (generic). (a) Chemical substance... zinc bis(dialkyldithiocarbamate) (PMN P-13-260) is subject to reporting under this section for...

  6. 40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this...

  7. 40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this...

  8. 40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this...

  9. 40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this...

  10. 40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this...

  11. New bioactive 2,6-diacetylpyridine bis(p-chlorophenylthiosemicarbazone) ligand and its Pd(II) and Pt(II) complexes: synthesis, characterization, cytotoxic activity and DNA binding ability.

    PubMed

    Matesanz, Ana I; Hernández, Carolina; Souza, Pilar

    2014-09-01

    Preparation and characterization of 2,6-diacetylpyridine bis((4)N-p-chlorophenylthiosemicarbazone) ligand, H2L, and its palladium(II) and platinum(II) complexes [PdL] and [PtL], is described. The molecular structure of the two new complexes has been determined by single crystal X-ray diffraction. The ligand acts as dianionic tetradentate donor coordinating to the metal center in a square planar geometry through the pyridine nitrogen atom and the azomethine nitrogen and thione sulfur atoms from one thiosemicarbazone arm, the fourth coordination position is occupied by the hydrazine nitrogen atom of the other arm. New free ligand and its metal complexes have been evaluated for antiproliferative activity in vitro against NCI-H460, T-47D, A2780 and A2780cisR human cancer cell lines. The cytotoxicity data suggest that these compounds may be endowed with important antitumor properties, especially H2L and [PtL] since they are capable of not only circumvent cisplatin resistance in A2780cisR cells but also exhibit high antiproliferative activity in breast cancer T-47D cells. The interaction of H2L with calf thymus DNA was also investigated and its binding constant (Kb) determined.

  12. Anti-plasmodial activity of aroylhydrazone and thiosemicarbazone iron chelators: effect on erythrocyte membrane integrity, parasite development and the intracellular labile iron pool.

    PubMed

    Walcourt, Asikiya; Kurantsin-Mills, Joseph; Kwagyan, John; Adenuga, Babafemi B; Kalinowski, Danuta S; Lovejoy, David B; Lane, Darius J R; Richardson, Des R

    2013-12-01

    Iron chelators inhibit the growth of the malaria parasite, Plasmodium falciparum, in culture and in animal and human studies. We previously reported the anti-plasmodial activity of the chelators, 2-hydroxy-1-naphthylaldehyde isonicotinoyl hydrazone (311), 2-hydroxy-1-naphthylaldehyde 4-methyl-3-thiosemicarbazone (N4mT), and 2-hydroxy-1-naphthylaldehyde 4-phenyl-3-thiosemicarbazone (N4pT). In fact, these ligands showed greater growth inhibition of chloroquine-sensitive (3D7) and chloroquine-resistant (7G8) strains of P. falciparum in culture compared to desferrioxamine (DFO). The present study examined the effects of 311, N4mT and N4pT on erythrocyte membrane integrity and asexual parasite development. While the characteristic biconcave disk shape of the erythrocytes was unaffected, the chelators caused very slight hemolysis at IC50 values that inhibited parasite growth. The chelators 311, N4mT and N4pT affected all stages of the intra-erythrocytic development cycle (IDC) of P. falciparum in culture. However, while these ligands primarily affected the ring-stage, DFO inhibited primarily trophozoite and schizont-stages. Ring, trophozoite and schizont-stages of the IDC were inhibited by significantly lower concentrations of 311, N4mT, and N4pT (IC50=4.45±1.70, 10.30±4.40, and 3.64±2.00μM, respectively) than DFO (IC50=23.43±3.40μM). Complexation of 311, N4mT and N4pT with iron reduced their anti-plasmodial activity. Estimation of the intracellular labile iron pool (LIP) in erythrocytes showed that the chelation efficacy of 311, N4mT and N4pT corresponded to their anti-plasmodial activities, suggesting that the LIP may be a potential source of non-heme iron for parasite metabolism within the erythrocyte. This study has implications for malaria chemotherapy that specifically disrupts parasite iron utilization.

  13. 40 CFR 721.10243 - Phosphonic acid, P-[2-[bis(2-hydroxyethyl)amino]ethyl]-, bis(2-chloroethyl) ester.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Phosphonic acid, P- ethyl]-, bis(2... Specific Chemical Substances § 721.10243 Phosphonic acid, P- ethyl]-, bis(2-chloroethyl) ester. (a... phosphonic acid, P- ethyl]-, bis(2-chloroethyl) ester (PMN P-09-193; CAS No. 55088-28-3) is subject...

  14. 40 CFR 721.10243 - Phosphonic acid, P-[2-[bis(2-hydroxyethyl)amino]ethyl]-, bis(2-chloroethyl) ester.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Phosphonic acid, P- ethyl]-, bis(2... Specific Chemical Substances § 721.10243 Phosphonic acid, P- ethyl]-, bis(2-chloroethyl) ester. (a... phosphonic acid, P- ethyl]-, bis(2-chloroethyl) ester (PMN P-09-193; CAS No. 55088-28-3) is subject...

  15. 40 CFR 721.10243 - Phosphonic acid, P-[2-[bis(2-hydroxyethyl)amino]ethyl]-, bis(2-chloroethyl) ester.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Phosphonic acid, P- ethyl]-, bis(2... Specific Chemical Substances § 721.10243 Phosphonic acid, P- ethyl]-, bis(2-chloroethyl) ester. (a... phosphonic acid, P- ethyl]-, bis(2-chloroethyl) ester (PMN P-09-193; CAS No. 55088-28-3) is subject...

  16. Bis(2-chloro-1-methylethyl) ether

    Integrated Risk Information System (IRIS)

    Bis ( 2 - chloro - 1 - methylethyl ) ether ; CASRN 108 - 60 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assess

  17. Bis-(5'-guanosyl) tetraphosphatase in rat tissues.

    PubMed Central

    Cameselle, J C; Costas, M J; Sillero, M A; Sillero, A

    1982-01-01

    The occurrence and distribution of bis-(5'-guanosyl) tetraphosphatase activity towards dinucleoside tetraphosphates between the 27 000 g supernatant and sedimented fraction were studied in liver, kidney, brain, muscle and intestinal mucosa from rat. The p1p4-bis-(5'-guanosyl) tetraphosphate-hydrolysing activities found in total homogenates were 0.77, 1.44, 0.39, 0.36 and 2.14 units (mumol/min)/g respectively. The activities found in the 27000 g-sedimented fractions were 74, 49, 11, 4 and 96% of those present in the homogenates respectively. The properties of the soluble enzymes were investigated. All of them have low Km values for p1p4-bis-(5'-guanosyl) tetraphosphate (from 2 to 50 microM), are competitively inhibited by guanosine 5'-tetraphosphate with K1 values from 10 to 160 nM, have molecular weights of about 21 000, require Mg2+ or Mn2+ and are inhibited by Ca2+. These properties show that bis-(5'-guanosyl) tetraphosphatase (EC 3.6.1.17), an enzyme previously characterized in Artemia salina and rat liver [Warner & Finamore (1965) Biochemistry 4, 1568-1575; Vallejo, Sillero & Sillero (1974) Biochim, Biophys. Acta 358, 117-125; Lobatón, Vallejo, Sillero & Sillero (1975) Eur. J. Biochem. 50, 495-501], is present in all the rat tissues examined. The inhibition of the enzyme by Ca2+ could be related to the effect of p1p4-bis-(5'-adenosyl) tetraphosphate as a trigger of DNA synthesis [Grummt, Waltl, Jantzen, Hamprecht, Huebscher & Kuenzle (1979) Proc. Natl. Acad. Sci. U.S.A. 76, 6081-6085]. PMID:6282267

  18. Bis-(5'-guanosyl) tetraphosphatase in rat tissues.

    PubMed

    Cameselle, J C; Costas, M J; Sillero, M A; Sillero, A

    1982-02-01

    The occurrence and distribution of bis-(5'-guanosyl) tetraphosphatase activity towards dinucleoside tetraphosphates between the 27 000 g supernatant and sedimented fraction were studied in liver, kidney, brain, muscle and intestinal mucosa from rat. The p1p4-bis-(5'-guanosyl) tetraphosphate-hydrolysing activities found in total homogenates were 0.77, 1.44, 0.39, 0.36 and 2.14 units (mumol/min)/g respectively. The activities found in the 27000 g-sedimented fractions were 74, 49, 11, 4 and 96% of those present in the homogenates respectively. The properties of the soluble enzymes were investigated. All of them have low Km values for p1p4-bis-(5'-guanosyl) tetraphosphate (from 2 to 50 microM), are competitively inhibited by guanosine 5'-tetraphosphate with K1 values from 10 to 160 nM, have molecular weights of about 21 000, require Mg2+ or Mn2+ and are inhibited by Ca2+. These properties show that bis-(5'-guanosyl) tetraphosphatase (EC 3.6.1.17), an enzyme previously characterized in Artemia salina and rat liver [Warner & Finamore (1965) Biochemistry 4, 1568-1575; Vallejo, Sillero & Sillero (1974) Biochim, Biophys. Acta 358, 117-125; Lobatón, Vallejo, Sillero & Sillero (1975) Eur. J. Biochem. 50, 495-501], is present in all the rat tissues examined. The inhibition of the enzyme by Ca2+ could be related to the effect of p1p4-bis-(5'-adenosyl) tetraphosphate as a trigger of DNA synthesis [Grummt, Waltl, Jantzen, Hamprecht, Huebscher & Kuenzle (1979) Proc. Natl. Acad. Sci. U.S.A. 76, 6081-6085].

  19. Halogen-free bis(imidazolium)/bis(ammonium)-di[bis(salicylato)borate] ionic liquids as energy-efficient and environmentally friendly lubricant additives.

    PubMed

    Gusain, Rashi; Gupta, Piyush; Saran, Sandeep; Khatri, Om P

    2014-09-10

    Bis(imidazolium)- and bis(ammonium)-di[bis(salicylato)borate] ionic liquids with variable alkyl chain and cyclic ring structures, were synthesized and then evaluated them as potential lubricant additives. The copper strip test results revealed noncorrosive properties of these ionic liquids. Introduction of halogen content in bis(imidazolium) ionic liquid by replacement of bis(salicylato)borate (BScB) anion with hexafluorophosphate (PF6(-)), severely corroded the copper strip. Thermogravimetric results showed that bis(imidazolium) ionic liquids exhibited higher thermal stability than bis(ammonium) ionic liquids owing to compact structure provided by imidazolium rings, higher intermolecular interactions, smaller free volume and low steric hindrance. The lubrication properties of these ionic liquids as additives to synthetic lubricant poly(ethylene) glycol (PEG 200) were evaluated for steel balls. Results showed that bis(ammonium)- and bis(imidazolium)-(BScB)2 ionic liquids as additives significantly reduced both friction coefficient and wear of PEG 200. The structure of cations, particularly the variation in substituted alkyl chain length monitored the degree of reduction in friction and wear. The excellent lubrication properties were attributed to the formation of adsorbed tribo-thin film and tribochemical product during the tribo-contact. Being halogen-, phosphorus-, and sulfur-free, these ionic liquids (a) protects contact surfaces from tribo-corrosive events, (b) reduces the friction and wear, and (c) keep environment green and clean.

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

    SciTech Connect

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

    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).

  1. Evaluation of DNA-binding, DNA cleavage, antioxidant and cytotoxic activity of mononuclear ruthenium(II) carbonyl complexes of benzaldehyde 4-phenyl-3-thiosemicarbazones

    NASA Astrophysics Data System (ADS)

    Sampath, Krishnan; Sathiyaraj, Subbaiyan; Jayabalakrishnan, Chinnasamy

    2013-11-01

    Two 4-phenyl-3-thiosemicarbazone ligands, (E)-2-(2-chlorobenzylidene)-N-phenylhydrazinecarbothioamide (HL1) and (E)-2-(2-nitrobenzylidene)-N-phenylhydrazinecarbothioamide (HL2), and its ruthenium(II) complexes were synthesized and characterized by physico-chemical and spectroscopic methods. The Schiff bases act as bidentate, monobasic chelating ligands with S and N as the donor sites and are preferably found in the thiol form in all the complexes studied. The molecular structure of HL1 and HL2 were determined by single crystal X-ray diffraction method. DNA binding of the compounds was investigated by absorption spectroscopy which indicated that the compounds bind to DNA via intercalation. The oxidative cleavage of the complexes with CT-DNA inferred that the effects of cleavage are dose dependent. Antioxidant study of the ligands and complexes showed significant antioxidant activity against DPPH radical. In addition, the in vitro cytotoxicity of the ligands and complexes assayed against HeLa and MCF-7 cell lines showed higher cytotoxic activity with the lower IC50 values indicating their efficiency in killing the cancer cells even at low concentrations.

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

    PubMed

    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.

  3. DNA, protein binding, cytotoxicity, cellular uptake and antibacterial activities of new palladium(II) complexes of thiosemicarbazone ligands: effects of substitution on biological activity.

    PubMed

    Kalaivani, P; Prabhakaran, R; Dallemer, F; Poornima, P; Vaishnavi, E; Ramachandran, E; Padma, V Vijaya; Renganathan, R; Natarajan, K

    2012-01-01

    The coordination propensities of 4(N,N')-diethylaminosalicylaldehyde-4(N)-substituted thiosemicarbazones (H(2)L(1-4)) were investigated by reacting with an equimolar amount of [PdCl(2)(PPh(3))(2)]. The new complexes were characterized by various spectroscopic techniques. The structure determination of the complexes [Pd(DeaSal-tsc)(PPh(3))] (1), [Pd(DeaSal-mtsc)(PPh(3))] (2) and [Pd(DeaSal-etsc)(PPh(3))] (3) by X-ray crystallography showed that ligands are coordinated in a dibasic tridentate ONS donor fashion forming stable five and six membered chelate rings. The binding ability of complexes (1-4) to calf-thymus DNA (CT DNA) has been explored by absorption and emission titration methods. Based on the observations, an electrostatic and an intercalative binding mode have been proposed. The protein binding studies have been monitored by quenching of tryptophan and tyrosine residues in the presence of complexes using lysozyme as a model protein. As determined by MTT assays, complex 3 exhibited a higher cytotoxic effect towards human lung cancer cell line (A549) and liver cancer cells (HepG2). LDH, NO assay and cellular uptake of the complexes have been studied. Further, antibacterial activity studies of the complexes have been screened against the pathogenic bacteria such as Enterococcus faecalis, Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa, MIC50 values of the complexes showed that the complexes exhibited significant activity against the pathogens and among the complexes, 3 exhibited higher activity.

  4. Spectroscopic characterization, antioxidant and antitumour studies of novel bromo substituted thiosemicarbazone and its copper(II), nickel(II) and palladium(II) complexes

    NASA Astrophysics Data System (ADS)

    Jagadeesh, M.; Lavanya, M.; Kalangi, Suresh K.; Sarala, Y.; Ramachandraiah, C.; Varada Reddy, A.

    2015-01-01

    A new, slightly distorted octahedral complex of copper(II), square planar complexes of nickel(II) and palladium(II) with 2,4‧-dibromoacetophenone thiosemicarbazone (DBAPTSC) are synthesized. The ligand and the complexes are characterized by FT-IR, FT-Raman, powder X-ray diffraction studies. The IR and Raman data are correlated for the presence of the functional groups which specifically helped in the confirmation of the compounds. In addition, the free ligand is unambiguously characterized by 1H and 13C NMR spectroscopy while the copper(II) complex is characterized by electron paramagnetic resonance spectroscopy (EPR). The g values for the same are found to be 2.246 (g1), 2.012 (g2) and 2.005 (g3) which suggested rhombic distortions. The HOMO-LUMO band gap calculations for these compounds are found to be in between 0.5 and 4.0 eV and these compounds are identified as semiconducting materials. The synthesized ligand and its copper(II), nickel(II) and palladium(II) complexes are subjected to antitumour activity against the HepG2 human hepatoblastoma cell lines. Among all the compounds, nickel(II) complex is found to exert better antitumour activity with 57.6% of cytotoxicity.

  5. Computational study of the vibrational spectroscopic studies, natural bond orbital, frontier molecular orbital and second-order non-linear optical properties of acetophenone thiosemicarbazone molecule.

    PubMed

    Li, Xiao-Hong; Mei, Zheng; Zhang, Xian-Zhou

    2014-01-24

    The vibrational frequencies of acetophenone thiosemicarbazone in the ground state have been calculated using density functional method (B3LYP) with 6-31G(d), 6-31G(d,p) and 6-311++G(d,p) basis sets. The analysis of natural bond orbital was also performed. The IR spectra were obtained and interpreted by means of potential energies distributions (PEDs) using MOLVIB program. In addition, the results show that there exist N-H…N and N-H…S hydrogen bonds in the title compound, which play a major role in stabilizing the molecule and are confirmed by the natural bond orbital analysis. The predicted NLO properties show that the title compound is a good candidate as second-order NLO material. In addition, the frontier molecular orbitals were analyzed and the crystal structure obtained by molecular mechanics belongs to the Pbca space group, with lattice parameters Z=8, a=16.0735 Å, b=7.1719 Å, c=7.8725 Å, ρ=0.808 g/cm(3).

  6. Simultaneous Determination of Cobalt(II) and Nickel(II) by Fourth-Order Derivative Spectrophotometric Method Using 2-Hydroxy-3-Methoxy Benzaldehyde Thiosemicarbazone

    PubMed Central

    Kumar, A. Praveen; Reddy, P. Raveendra; Reddy, V. Krishna

    2007-01-01

    A simple and new simultaneous fourth derivative spectrophotometric method is proposed for the analysis of a two-component system containing cobalt(II) and nickel(II) without separation using 2-hydroxy-3-methoxy benzaldehyde thiosemicarbazone (HMBATSC) as a chromophoric reagent. The reagent reacts with cobalt(II) and nickel(II) at pH 6.0, forming soluble brown and yellow colored species, respectively. Cobalt(II) and nickel(II) present in themixture are simultaneously determined without solving the simultaneous equations bymeasuring the fourth derivative amplitudes at 468.5 nm and 474.5 nm, respectively. The derivative amplitudes obey Beer's law at 468.5 nm and 474.5 nm for Co(II) and Ni(II) in the range 0.059–3.299 μg mL−1 and 0.058–3.285 μg mL−1 respectively. A large number of foreign ions do not interfere in the present method. The present simultaneous method is used for the determination of micro amounts of cobalt in biological samples, nickel in plant samples, and in some alloy steels and soil sample. PMID:17671609

  7. Synthesis of a DNA-targeting nickel (II) complex with testosterone thiosemicarbazone which exhibits selective cytotoxicity towards human prostate cancer cells (LNCaP).

    PubMed

    Heng, Mok Piew; Sinniah, Saravana Kumar; Teoh, Wuen Yew; Sim, Kae Shin; Ng, Seik Weng; Cheah, Yoke Kqueen; Tan, Kong Wai

    2015-01-01

    Testosterone thiosemicarbazone, L and its nickel (II) complex 1 were synthesized and characterized by using FTIR, CHN, (1)H NMR, and X-ray crystallography. X-ray diffraction study confirmed the formation of L from condensation of testosterone and thiosemicarbazide. Mononuclear complex 1 is coordinated to two Schiff base ligands via two imine nitrogens and two tautomeric thiol sulfurs. The cytotoxicity of both compounds was investigated via MTT assay with cisplatin as positive reference standard. L is more potent towards androgen-dependent LNCaP (prostate) and HCT 116 (colon). On the other hand, complex 1, which is in a distorted square planar environment with L acting as a bidentate NS-donor ligand, is capable of inhibiting the growth of all the cancer cell lines tested, including PC-3 (prostate). It is noteworthy that both compounds are less toxic towards human colon cell CCD-18Co. The intrinsic DNA binding constant (Kb) of both compounds were evaluated via UV-Vis spectrophotometry. Both compounds showed Kb values which are comparable to the reported Kb value of typical classical intercalator such as ethidium bromide. The binding constant of the complex is almost double compared with ligand L. Both compounds were unable to inhibit the action topoisomerase I, which is the common target in cancer treatment (especially colon cancer). This suggest a topoisomerase I independent-cell death mechanism.

  8. Thiosemicarbazone p-Substituted Acetophenone Derivatives Promote the Loss of Mitochondrial Δψ, GSH Depletion, and Death in K562 Cells

    PubMed Central

    Pessoto, Felipe S.; Yokomizo, Cesar H.; Prieto, Tatiana; Fernandes, Cleverton S.; Silva, Alan P.; Kaiser, Carlos R.; Basso, Ernani A.; Nantes, Iseli L.

    2015-01-01

    A series of thiosemicarbazone (TSC) p-substituted acetophenone derivatives were synthesized and chemically characterized. The p-substituents appended to the phenyl group of the TSC structures were hydrogen, fluor, chlorine, methyl, and nitro, producing compounds named TSC-H, TSC-F, TSC-Cl, TSC-Me, and TSC-NO2, respectively. The TSC compounds were evaluated for their capacity to induce mitochondrial permeability, to deplete mitochondrial thiol content, and to promote cell death in the K562 cell lineage using flow cytometry and fluorescence microscopy. TSC-H, TSC-F, and TSC-Cl exhibited a bell-shaped dose-response curve for the induction of apoptosis in K562 cells due to the change from apoptosis to necrosis as the principal mechanism of cell death at the highest tested doses. TSC-Me and TSC-NO2 exhibited a typical dose-response profile, with a half maximal effective concentration of approximately 10 µM for cell death. Cell death was also evaluated using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, which revealed lower toxicity of these compounds for peripheral blood mononuclear cells than for K562 cells. The possible mechanisms leading to cell death are discussed based on the observed effects of the new TSC compounds on the cellular thiol content and on mitochondrial bioenergetics. PMID:26075034

  9. Synthesis, spectral characterization and biological activities of Mn(II) and Co(II) complexes with benzyloxybenzaldehyde-4-phenyl-3-thiosemicarbazone.

    PubMed

    Prathima, B; Rao, Y Subba; Ramesh, G N; Jagadeesh, M; Reddy, Y P; Chalapathi, P V; Reddy, A Varada

    2011-06-01

    Mn(II) and Co(II) complexes of benzyloxybenzaldehyde-4-phenyl-3-thiosemicarbazone have been synthesized and characterized by the investigations of electronic and EPR spectra and X-ray diffraction. Based on the spectral studies, an octahedral geometry is assigned for the Mn(II) and Co(II) complexes. X-ray powder diffraction studies reveal that Mn(II) and Co(II) complexes have triclinic crystal lattices. The unit cell parameters of the Mn(II) complex are a=11.0469 Å, b=6.2096 Å, c=7.4145 Å, α=90.646°, β=95.127°, γ=104.776°, V=489.7 Å(3) and those of Co(II) complex are a=9.3236 Å, b=10.2410 Å, c=7.8326 Å, α=90.694°, β=99.694°, γ=100.476°, V=724.2 Å(3). When the free ligand and its metal complexes are subjected to antibacterial activity, the metal complexes are proved to be more active than the ligand. However with regard to in vitro antioxidant activity, the ligand exhibits greater antioxidant activity than its metal(II) complexes.

  10. Spectroscopic (FT-IR, FT-Raman) and quantum mechanical studies of 3t-pentyl-2r,6c-diphenylpiperidin-4-one thiosemicarbazone.

    PubMed

    Savithiri, S; Arockia doss, M; Rajarajan, G; Thanikachalam, V; Bharanidharan, S; Saleem, H

    2015-02-05

    In this study, the molecular structure and vibrational spectra of 3t-pentyl2r,6c-diphenylpiperidin-4-one thiosemicarbazone (PDPOTSC) were studied. The ground-state molecular geometry was ascertained by using the density functional theory (DFT)/B3LYP method using 6-31++G(d,p) as a basis set. The vibrational (FT-IR and FT-Raman) spectra of PDPOTSC were computed using DFT/B3LYP and HF methods with 6-31++G(d,p) basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED⩾10%) of the vibrational modes, calculated with scaled quantum mechanics (SQM) methods PQS program. The electrical dipole moment (μ) and first hyperpolarizability (βo) values have been computed using DFT/B3LYP and HF methods. The calculated result (βo) shows that the title molecule might have nonlinear optical (NLO) behavior. Atomic charges of C, N, S and molecular electrostatic potential (MEP) were calculated using B3LYP/6-31G++(d,p). The HOMO-LUMO energies were calculated and natural bonding orbital (NBO) analysis has also been carried out.

  11. Spectroscopic (FT-IR, FT-Raman) and quantum mechanical studies of 3t-pentyl-2r,6c-diphenylpiperidin-4-one thiosemicarbazone

    NASA Astrophysics Data System (ADS)

    Savithiri, S.; Arockia doss, M.; Rajarajan, G.; Thanikachalam, V.; Bharanidharan, S.; Saleem, H.

    2015-02-01

    In this study, the molecular structure and vibrational spectra of 3t-pentyl2r,6c-diphenylpiperidin-4-one thiosemicarbazone (PDPOTSC) were studied. The ground-state molecular geometry was ascertained by using the density functional theory (DFT)/B3LYP method using 6-31++G(d,p) as a basis set. The vibrational (FT-IR and FT-Raman) spectra of PDPOTSC were computed using DFT/B3LYP and HF methods with 6-31++G(d,p) basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED ⩾ 10%) of the vibrational modes, calculated with scaled quantum mechanics (SQM) methods PQS program. The electrical dipole moment (μ) and first hyperpolarizability (βo) values have been computed using DFT/B3LYP and HF methods. The calculated result (βo) shows that the title molecule might have nonlinear optical (NLO) behavior. Atomic charges of C, N, S and molecular electrostatic potential (MEP) were calculated using B3LYP/6-31G++(d,p). The HOMO-LUMO energies were calculated and natural bonding orbital (NBO) analysis has also been carried out.

  12. 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.

    PubMed

    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.

  13. 40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alphaâ²- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721.9663 Section 721.9663 Protection...(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. (a... poly(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl)...

  14. 40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alphaâ²- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721.9663 Section 721.9663 Protection...(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. (a... poly(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl)...

  15. 40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alphaâ²- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721.9663 Section 721.9663 Protection...(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. (a... poly(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl)...

  16. 40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alphaâ²- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721.9663 Section 721.9663 Protection...(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. (a... poly(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl)...

  17. 40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alphaâ²- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721.9663 Section 721.9663 Protection...(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. (a... poly(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl)...

  18. Novel Thiosemicarbazones Inhibit Lysine-Rich CEACAM1 Co-isolated (LYRIC) and the LYRIC-Induced Epithelial-Mesenchymal Transition via Up-Regulation of N-Myc Downstream-Regulated Gene 1 (NDRG1).

    PubMed

    Xi, Ruxing; Pun, Ivan Ho Yuen; Menezes, Sharleen V; Fouani, Leyla; Kalinowski, Danuta S; Huang, Michael L H; Zhang, Xiaozhi; Richardson, Des R; Kovacevic, Zaklina

    2017-03-08

    Tumor necrosis factor α (TNFα) plays a vital role in cancer progression, being associated with inflammation and promotion of cancer angiogenesis and metastasis. The effects of TNFα are mediated by its down-stream target, the oncogene, lysine-rich CEACAM1 co-isolated protein (LYRIC; also known as metadherin or astrocyte elevated gene-1). LYRIC plays an important role in activating the nuclear factor-κB (NF-κB) signaling pathway, which controls multiple cellular processes, including proliferation, apoptosis, migration, etc. In contrast, the metastasis suppressor, N-myc down-stream regulated gene 1 (NDRG1), has the opposite effect on the NF-κB pathway, being able to inhibit NF-κB activation and reduce angiogenesis, proliferation, migration and cancer cell invasion. These potent anti-cancer properties make NDRG1 an ideal therapeutic target. Indeed, a novel class of thiosemicarbazone anti-cancer agents that target this molecule have been developed, with the lead agent, di-2-pyridylketone 4-cyclohexyl-4-methyl-3-thiosemicarbazone (DpC), recently entering clinical trials for advanced and resistant cancers. To further elucidate the interaction between NDRG1 and oncogenic signaling, this study for the first time assessed the effects of NDRG1 on the tumorigenic properties of TNFα and its down-stream target, LYRIC. We demonstrate that NDRG1 inhibits the TNFα-mediated epithelial to mesenchymal transition (EMT). Further, NDRG1 also potently inhibited LYRIC expression, with a negative feedback loop existing between these two molecules. Examining the mechanism involved, we demonstrated that NDRG1 inhibited PI3K/AKT signaling, leading to reduced levels of the LYRIC transcriptional activator, c-Myc. Finally, we demonstrate that novel thiosemicarbazones that up-regulate NDRG1 also inhibit LYRIC expression, further highlighting their marked potential for cancer treatment.

  19. Halo-substituted thiosemicarbazones and their copper(II), nickel(II) complexes: detailed spectroscopic characterization and study of antitumour activity against HepG2 human hepatoblastoma cells.

    PubMed

    Jagadeesh, M; Kalangi, Suresh K; Sivarama Krishna, L; Reddy, A Varada

    2014-01-24

    Copper(II) and nickel(II) complexes of two different halogen substituted thiosemicarbazone ligands were synthesized. The ligands 3,4-difluoroacetophenone thiosemicarbazone (1) and 2-bromo-4'-chloroacetophenone thiosemicarbazone (2) were characterized and confirmed spectroscopically by FT-IR, FT-Raman, UV-vis and fluorescence spectral analysis, while the respective copper(II) complexes [Cu(C9H9N3F2S)2Cl2] (1a), [Cu(C9H9N3ClBrS)2Cl2] (2a) and nickel(II) complexes [Ni(C9H9N3F2S)2] (1b), [Ni(C9H9N3ClBrS)2] (2b) were characterized by FT-IR, UV-vis and electron paramagnetic spectroscopy (EPR). The EPR spectra of the Cu(II) complexes provided the rhombic octahedral and axial symmetry of the complexes 1a and 2a respectively. For the complex 1a, the g values calculated as g1=2.1228, g2=2.0706 and g3=2.001 between 2900 and 3300 G. While for the complex 2a, a set of two resonance absorptions were observed. The synthesized compounds were tested for antitumor activity and showed that the ability to kill liver cancer cells significantly. Out of all the synthesized compounds, copper(II) complexes 1a and 2a showed high cytotoxic effect on liver cancer cells with 67.51% and 42.77% of cytotoxicity respectively at 100 μM.

  20. Halo-substituted thiosemicarbazones and their copper(II), nickel(II) complexes: Detailed spectroscopic characterization and study of antitumour activity against HepG2 human hepatoblastoma cells

    NASA Astrophysics Data System (ADS)

    Jagadeesh, M.; Kalangi, Suresh K.; Sivarama Krishna, L.; Reddy, A. Varada

    2014-01-01

    Copper(II) and nickel(II) complexes of two different halogen substituted thiosemicarbazone ligands were synthesized. The ligands 3,4-difluoroacetophenone thiosemicarbazone (1) and 2-bromo-4'-chloroacetophenone thiosemicarbazone (2) were characterized and confirmed spectroscopically by FT-IR, FT-Raman, UV-vis and fluorescence spectral analysis, while the respective copper(II) complexes [Cu(C9H9N3F2S)2Cl2] (1a), [Cu(C9H9N3ClBrS)2Cl2] (2a) and nickel(II) complexes [Ni(C9H9N3F2S)2] (1b), [Ni(C9H9N3ClBrS)2] (2b) were characterized by FT-IR, UV-vis and electron paramagnetic spectroscopy (EPR). The EPR spectra of the Cu(II) complexes provided the rhombic octahedral and axial symmetry of the complexes 1a and 2a respectively. For the complex 1a, the g values calculated as g1 = 2.1228, g2 = 2.0706 and g3 = 2.001 between 2900 and 3300 G. While for the complex 2a, a set of two resonance absorptions were observed. The synthesized compounds were tested for antitumor activity and showed that the ability to kill liver cancer cells significantly. Out of all the synthesized compounds, copper(II) complexes 1a and 2a showed high cytotoxic effect on liver cancer cells with 67.51% and 42.77% of cytotoxicity respectively at 100 μM.

  1. Perioperative cerebral ischaemia in cardiac surgery and BIS.

    PubMed

    Villacorta, J; Kerbaul, F; Collart, F; Guidon, C; Bonnet, M; Guillen, J C; Gouin, F

    2005-08-01

    A 46-year-old woman was monitored by bispectral index monitoring (BIS) during redo aortic and mitral valve replacement. On release of the aortic cross clamp there was a sudden, severe, unexplained, and sustained fall in the BIS value. Postoperatively, a CT scan was consistent with multiple ischaemic lesions. The lesions were presumed to be due to air embolism. This case suggests that a sudden unexplained and persistent fall in BIS may indicate cerebral ischaemia.

  2. Bis(amidate)bis(amido) titanium complex: a regioselective intermolecular alkyne hydroamination catalyst.

    PubMed

    Yim, Jacky C-H; Bexrud, Jason A; Ayinla, Rashidat O; Leitch, David C; Schafer, Laurel L

    2014-03-07

    An efficient and selective bis(amidate)bis(amido) titanium precatalyst for the anti-Markovnikov hydroamination of alkynes is reported. Hydroamination of terminal and internal alkynes with primary alkylamines, arylamines, and hydrazines is promoted by 5-10 mol % of Ti catalyst. Various functional groups are tolerated including esters, protected alcohols, and imines. The in situ generated complex shows comparable catalytic activity, demonstrating its synthetic versatility for benchtop application. Applications of this catalyst for the synthesis of amino alcohols and a one-pot procedure for indole synthesis are described. A mechanistic proposal that invokes turnover-limiting protonolysis is presented to rationalize the observed regioselectivities.

  3. Intramolecular Electron Transfer in Bis(tetraalkyl Hydrazine) and Bis(hydrazyl) Radical Cations.

    NASA Astrophysics Data System (ADS)

    Chang, Hao

    A series of multicyclic bis(hydrazine) and bis(diazenium) compounds connected by relatively rigid hydrocarbon frameworks were prepared for the study of intramolecular electron transfer. The thermodynamics of electron removal of these compounds was investigated by cyclic voltammetry. The difference between the first and second oxidation potentials for the 4 sigma-bonded species was found to be larger for the bis(hydrazyl) radical systems than for the bis(hydrazines) by ca. 0.2 V (4.6 kcal/mol). This indicates a greater degree of interaction between the two nitrogen moieties for the hydrazyl systems, which is consistent with a greater degree of electronic coupling (H _{rm AB}) in these systems. The ESR spectra of the 4 sigma -bonded bis(hydrazine) radical cations indicate localized radical cations, which corresponds to slow intramolecular electron transfer on the ESR timescale. Conversely, the ESR spectra of the corresponding bis(hydrazyl) radical cation systems show nitrogen hyperfine splittings of a(4N) of ca. 4.5 G. This indicates that intramolecular electron transfer between the two nitrogen moieties is fast on the ESR timescale; the rate of exchange, k_ {rm ex} was estimated to be well above 1.9 times 10^8 s^{-1}. The contrast in exchange rates is consistent with the large geometry change upon oxidation which is characteristic of hydrazines. The hydrazyls undergo a smaller geometry change upon oxidation, and thus are expected to exhibit smaller inner-sphere reorganization energies. The optical spectra of these radical species was investigated in hopes of observing absorption bands corresponding to intramolecular electron transfer, as predicted by Hush theory. A broad absorption band was observed in the near IR region for the saturated bis(hydrazyl) radical cation system at 1060 nm (9420 cm^{-1} ) in acetonitrile at room temperature, and was accompanied by a narrower band at 1430 nm (6993 cm^ {-1}). The width of this band was estimated to be 545 nm (6496 cm^{-1

  4. Reactions of thiosemicarbazones derived from beta-keto amides and beta-keto esters with Zn(II) and Cd(II) acetates: influence of metal, substitution, reagent ratio and temperature on metal-induced cyclization.

    PubMed

    Casas, José S; Castaño, María V; García-Tasende, María S; Rodríguez-Castellón, Enrique; Sánchez, Agustín; Sanjuán, Luisa M; Sordo, José

    2004-07-07

    Zinc(II) and cadmium(II) acetates were reacted in methanol under various experimental conditions with thiosemicarbazones derived from beta-keto amides or beta-keto esters (HTSC). Some of these reactions afforded thiosemicarbazonate complexes [M(TSC)2] with IR and NMR spectra compatible with N,S-coordination, but most gave complexes [ML2], where HL is a substituted 2,5-dihydro-5-oxo-1H-pyrazole-1-carbothioamide resulting from cyclization of the HTSC. Some of these pyrazolonates and two of the HL ligands were studied by X-ray diffractometry, and their structures are discussed. Surprisingly, the reactions of zinc(II) acetate with HTSC in 1:1 mol ratio usually gave a third, previously unreported type of complex with a dideprotonated ligand, [Zn(L-H)], which was also formed when [ZnL2] and Zn(OAc)2 interacted at room temperature in 1:1 mol ratio. These L-H complexes are highly insoluble in all common solvents, which hinders their characterization but suggests that they are polymeric in nature.

  5. Ligational behavior of thiosemicarbazone, semicarbazone and thiocarbohydrazone ligands towards VO(IV), Ce(III), Th(IV) and UO 2(VI) ions: Synthesis, structural characterization and biological studies

    NASA Astrophysics Data System (ADS)

    Shebl, M.; Seleem, H. S.; El-Shetary, B. A.

    2010-01-01

    Mono- and binuclear VO(IV), Ce(III), Th(IV) and UO 2(VI) complexes of thiosemicarbazone, semicarbazone and thiocarbohydrazone ligands derived from 4,6-diacetylresorcinol were synthesized. The structures of these complexes were elucidated by elemental analyses, IR, UV-vis, ESR, 1H NMR and mass spectra as well as conductivity and magnetic susceptibility measurements and thermal analyses. The thiosemicarbazone (H 4L 1) and the semicarbazone (H 4L 2) ligands behave as dibasic pentadentate ligands in case of VO(IV) and UO 2(VI) complexes, tribasic pentadentate in case of Ce(III) complexes and monobasic pentadentate in case of Th(IV) complexes. However, the thiocarbohydrazone ligand (H 3L 3) acts as a monobasic tridentate ligand in all complexes except the VO(IV) complex in which it acts as a dibasic tridentate ligand. The antibacterial and antifungal activities were also tested against Rhizobium bacteria and Fusarium-Oxysporium fungus. The metal complexes of H 4L 1 ligand showed a higher antibacterial effect than the free ligand while the other ligands (H 4L 2 and H 3L 3) showed a higher effect than their metal complexes. The antifungal effect of all metal complexes is lower than the free ligands.

  6. 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.

    PubMed

    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.

  7. 40 CFR 721.5760 - Phenol, 4,4′-[methylene-bis (oxy-2,1-ethanediylthio)]bis-.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Phenol, 4,4â²- bis-. 721.5760 Section... Substances § 721.5760 Phenol, 4,4′- bis-. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance phenol, 4,4′- bis- (PMN P-87-1760) is subject to reporting under...

  8. 21 CFR 73.3100 - 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...)ester copolymers. 73.3100 Section 73.3100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF... § 73.3100 1,4-Bis -9,10-anthracenedione bis(2-propenoic)ester copolymers. (a) Identity. The color additives are 1,4-bis -9,10-anthracenedione bis(2-propenoic)ester (CAS Reg. No. 109561-07-1)...

  9. 21 CFR 73.3100 - 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...)ester copolymers. 73.3100 Section 73.3100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF... § 73.3100 1,4-Bis -9,10-anthracenedione bis(2-propenoic)ester copolymers. (a) Identity. The color additives are 1,4-bis -9,10-anthracenedione bis(2-propenoic)ester (CAS Reg. No. 109561-07-1)...

  10. 40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...)]bis-, bis(4-methylbenzene sulfonate); and ethanol, 2- oxy]ethoxy] ethoxy]methyl]-2-(2-propenyloxy...-methylbenzene sulfonate); and ethanol, 2- oxy]ethoxy] ethoxy]methyl]-2-(2-propenyloxy)ethoxy]-, 4...-methylbenzene-sulfonate) (PMN P-93-1195, CAS no. 19249-03-7), ethanol, 2,2′- bis-, bis(4-methylbenzene...

  11. 40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...)]bis-, bis(4-methylbenzene sulfonate); and ethanol, 2- oxy]ethoxy] ethoxy]methyl]-2-(2-propenyloxy...-methylbenzene sulfonate); and ethanol, 2- oxy]ethoxy] ethoxy]methyl]-2-(2-propenyloxy)ethoxy]-, 4...-methylbenzene-sulfonate) (PMN P-93-1195, CAS no. 19249-03-7), ethanol, 2,2′- bis-, bis(4-methylbenzene...

  12. Exploring the Anti-Cancer Activity of Novel Thiosemicarbazones Generated through the Combination of Retro-Fragments: Dissection of Critical Structure-Activity Relationships

    PubMed Central

    Rasko, Nathalie; Potůčková, Eliška; Mrozek-Wilczkiewicz, Anna; Musiol, Robert; Małecki, Jan G.; Sajewicz, Mieczysław; Ratuszna, Alicja; Muchowicz, Angelika; Gołąb, Jakub; Šimůnek, Tomáš; Richardson, Des R.; Polanski, Jaroslaw

    2014-01-01

    Thiosemicarbazones (TSCs) are an interesting class of ligands that show a diverse range of biological activity, including anti-fungal, anti-viral and anti-cancer effects. Our previous studies have demonstrated the potent in vivo anti-tumor activity of novel TSCs and their ability to overcome resistance to clinically used chemotherapeutics. In the current study, 35 novel TSCs of 6 different classes were designed using a combination of retro-fragments that appear in other TSCs. Additionally, di-substitution at the terminal N4 atom, which was previously identified to be critical for potent anti-cancer activity, was preserved through the incorporation of an N4-based piperazine or morpholine ring. The anti-proliferative activity of the novel TSCs were examined in a variety of cancer and normal cell-types. In particular, compounds 1d and 3c demonstrated the greatest promise as anti-cancer agents with potent and selective anti-proliferative activity. Structure-activity relationship studies revealed that the chelators that utilized “soft” donor atoms, such as nitrogen and sulfur, resulted in potent anti-cancer activity. Indeed, the N,N,S donor atom set was crucial for the formation of redox active iron complexes that were able to mediate the oxidation of ascorbate. This further highlights the important role of reactive oxygen species generation in mediating potent anti-cancer activity. Significantly, this study identified the potent and selective anti-cancer activity of 1d and 3c that warrants further examination. PMID:25329549

  13. Spectrophotometric, voltammetric and cytotoxicity studies of 2-hydroxy-5-methoxyacetophenone thiosemicarbazone and its N(4)-substituted derivatives: A combined experimental-computational study

    NASA Astrophysics Data System (ADS)

    Akgemci, Emine Guler; Saf, Ahmet Ozgur; Tasdemir, Halil Ugur; Türkkan, Ercan; Bingol, Haluk; Turan, Suna Ozbas; Akkiprik, Mustafa

    2015-02-01

    In this study, 2-hydroxy-5-methoxyacetophenone thiosemicarbazone (HMAT) and its novel N(4) substituted derivatives were synthesized and characterized by different techniques. The optical band gap of the compounds and the energy of HOMO were experimentally examined by UV-vis spectra and cyclic voltammetry measurements, respectively. Furthermore, the conformational spaces of the compounds were scanned with molecular mechanics method. The geometry optimization, HOMO and LUMO energies, the energy gap of the HOMO-LUMO, dipole moment of the compounds were theoretically calculated by the density functional theory B3LYP/6-311++G(d,p) level. The minimal electronic excitation energy and maximum wavelength calculations of the compounds were also performed by TD-DFT//B3LYP/6-311++G(d,p) level of theory. Theoretically calculated values were compared with the related experimental values. The combined results exhibit that all compounds have good electron-donor properties which affect anti-proliferative activity. The cytotoxic effects of the compounds were also evaluated against HeLa (cervical carcinoma), MCF-7 (breast carcinoma) and PC-3 (prostatic carcinoma) cell lines using the standard MTT assay. All tested compounds showed antiproliferative effect having IC50 values in different range. In comparison with that of HMAT, it was obtained that while ethyl group on 4(N)-substituted position decreased in potent anti-proliferative effect, the phenyl group on the position increased in anti-proliferative effect for the tested cancer cell line. Considering the molecular energy parameters, the cytotoxicity activities of the compounds were discussed.

  14. Development of highly sensitive extractive spectrophotometric determination of nickel(II) in medicinal leaves, soil, industrial effluents and standard alloy samples using pyridoxal-4-phenyl-3-thiosemicarbazone.

    PubMed

    Sarma, Loka Subramanyam; Kumar, Jyothi Rajesh; Reddy, Koduru Janardhan; Thriveni, Thenepalli; Reddy, Ammireddy Varada

    2008-01-01

    Pyridoxal-4-phenyl-3-thiosemicarbazone (PPT) is proposed as a new sensitive reagent for the extractive spectrophotometric determination of nickel(II). PPT reacts with nickel(II) in the pH range 4.0-6.0 to form a reddish brown colored complex, which was well-extracted into n-butanol. The absorbance value of the Ni(II)-PPT complex was measured at different time intervals at 430nm, to ascertain the stability of the complex. The system obeyed Beer's law up to 0.5-5.0microgmL(-1) of nickel(II), with an excellent linearity in terms of the correlation coefficient value of 0.99. The molar absorptivity and Sandell's sensitivity of the extracted species are 1.92 x 10(4)Lmol(-1)cm(-1) and 0.003057microgcm(-2) respectively at 430nm. The detection limit of the method is 0.069microgmL(-1). To assess precision and accuracy of the developed method, determinations were carried out at different concentrations. The relative standard deviation of all measurements does not exceed 2.62%. The developed method has been satisfactorily applied for the determination of nickel(II), when present alone or in the presence of diverse ions, which are usually associated with nickel(II) in medicinal leaves, soil and industrial effluent samples. Various standard and certified reference materials (CM 247 LC, IN 718, BCS 233, 266, 253 and 251) have also been tested for the determination of nickel for the purpose of validation of the present method. The results of the proposed method are compared with those obtained from an atomic absorption spectrometer (AAS).

  15. Antiviral activity against the hepatitis C virus (HCV) of 1-indanone thiosemicarbazones and their inclusion complexes with hydroxypropyl-β-cyclodextrin.

    PubMed

    Glisoni, Romina J; Cuestas, María L; Mathet, Verónica L; Oubiña, José R; Moglioni, Albertina G; Sosnik, Alejandro

    2012-10-09

    The hepatitis C virus (HCV) is a major cause of acute and chronic hepatitis in humans. Approximately 5% of the infected people die from cirrhosis or hepatocellular carcinoma. The current standard therapy comprises a combination of pegylated-interferon alpha and ribavirin. Due to the relatively low effectiveness, the prohibitive costs and the extensive side effects of the treatment, an intense research for new direct-acting anti-HCV agents is taking place. Furthermore, NS3 protease inhibitors recently introduced into the market are not effective against all HCV subgenotypes. Thiosemicarbazones (TSCs) have shown antiviral activity against a wide range of DNA and RNA viruses. However, their extremely low aqueous solubility and high self-aggregation tendency often preclude their reliable biological evaluation in vitro. In this work, we investigated and compared for the first time the anti-HCV activity of two 1-indanone TSCs, namely 5,6-dimethoxy-1-indanone TSC and 5,6-dimethoxy-1-indanone N4-allyl TSC, and their inclusion complexes with hydroxypropyl-β-cyclodextrin (HPβ-CD) in Huh-7.5 cells containing the full-length and the subgenomic subgenotype 1b HCV replicon system. Studies of physical stability in culture medium showed that free TSCs precipitated rapidly and formed submicron aggregates. Conversely, TSC complexation with HPβ-CD led to more stable systems with minimal size growth and drug concentration loss. More importantly, both TSCs and their inclusion complexes displayed a potent suppression of the HCV replication in both cell lines with no cytotoxic effects. The mechanism likely involves the inhibition of non-structural proteins of the virus. In addition, findings suggested that the cyclodextrin released the drug to the culture medium over time. This platform could be exploited for the study of the drug toxicity and pharmacokinetics animal models.

  16. Evidence for dual mode of action of a thiosemicarbazone, NSC73306: A potent substrate of the multidrug resistance-linked ABCG2 transporter

    PubMed Central

    Wu, Chung-Pu; Shukla, Suneet; Calcagno, Anna Maria; Hall, Matthew D.; Gottesman, Michael M.; Ambudkar, Suresh V.

    2008-01-01

    Multidrug resistance due to reduced drug accumulation is a phenomenon predominantly caused by the overexpression of members of the ATP-binding cassette transporters, including ABCB1 (P-glycoprotein), ABCG2 and several ABCC family members (MRPs). We previously reported that a thiosemicarbazone derivative, NSC73306, is cytotoxic to carcinoma cells that overexpress functional P-glycoprotein and it re-sensitizes these cells to chemotherapeutics. In this study, we investigated the effect of NSC73306 on cells overexpressing other ABC drug transporters, including ABCG2, MRP1, MRP4 and MRP5. Our findings demonstrated that NSC73306 is not more toxic to cells that overexpress these transporters compared to their respective parental cells, and these transporters do not confer resistance to NSC73306 either. In spite of this, we observed that NSC73306 is a transport substrate for ABCG2 that can effectively inhibit ABCG2-mediated drug transport and reverse resistance to both mitoxantrone and topotecan in ABCG2-expressing cells. Interactions between NSC73306 and the ABCG2 drug-binding site(s) were confirmed by its stimulatory effect on ATPase activity (140–150 nM concentration required for 50% stimulation) and by inhibition of [125I]-Iodoarylazidoprazosin photolabeling (50% inhibition at 250–400 nM) of the substrate-binding site(s). Overall, NSC73306 appears to be a potent modulator of ABCG2 that does not interact with MRP1, MRP4 or MRP5. Collectively, these data suggest that NSC73306 can potentially be used, due to its dual mode of action, as an effective agent to overcome drug resistance by eliminating P-glycoprotein-overexpressing cells, and by acting as a potent modulator that re-sensitizes ABCG2-expressing cancer cells to chemotherapeutics. PMID:18089722

  17. Uptake of compounds that selectively kill multidrug-resistant cells: the copper transporter SLC31A1 (CTR1) increases cellular accumulation of the thiosemicarbazone NSC73306.

    PubMed

    Fung, King Leung; Tepede, Abisola K; Pluchino, Kristen M; Pouliot, Lynn M; Pixley, Jessica N; Hall, Matthew D; Gottesman, Michael M

    2014-08-04

    Acquired drug resistance in cancer continues to be a challenge in cancer therapy, in part due to overexpression of the drug efflux transporter P-glycoprotein (P-gp, MDR1, ABCB1). NSC73306 is a thiosemicarbazone compound that displays greater toxicity against cells expressing functional P-gp than against other cells. Here, we investigate the cellular uptake of NSC73306, and examine its interaction with P-gp and copper transporter 1 (CTR1, SLC31A1). Overexpression of P-gp sensitizes LLC-PK1 cells to NSC73306. Cisplatin (IC50 = 77 μM), cyclosporin A (IC50 = 500 μM), and verapamil (IC50 = 700 μM) inhibited cellular accumulation of [(3)H]NSC73306. Cellular hypertoxicity of NSC73306 to P-gp-expressing cells was inhibited by cisplatin in a dose-dependent manner. Cells transiently expressing the cisplatin uptake transporter CTR1 (SLC31A1) showed increased [(3)H]NSC73306 accumulation. In contrast, CTR1 knockdown decreased [(3)H]NSC73306 accumulation. The presence of NSC73306 reduced CTR1 levels, similar to the negative feedback of CTR1 levels by copper or cisplatin. Surprisingly, although cisplatin is a substrate of CTR1, we found that CTR1 protein was overexpressed in high-level cisplatin-resistant KB-CP20 and BEL7404-CP20 cell lines. We confirmed that the CTR1 protein was functional, as uptake of NSC73306 was increased in KB-CP20 cells compared to their drug-sensitive parental cells, and downregulation of CTR1 in KB-CP20 cells reduced [(3)H]NSC73306 accumulation. These results suggest that NSC73306 is a transport substrate of CTR1.

  18. Synthesis, characterization, and preliminary in vitro studies of vanadium(IV) complexes with a Schiff base and thiosemicarbazones as mixed-ligands.

    PubMed

    Lewis, Nerissa A; Liu, Fange; Seymour, Luke; Magnusen, Anthony; Erves, Travis R; Arca, Jessa Faye; Beckford, Floyd A; Venkatraman, Ramaiyer; González-Sarrías, Antonio; Fronczek, Frank R; Vanderveer, Don G; Seeram, Navindra P; Liu, Aimin; Jarrett, William L; Holder, Alvin A

    2012-02-01

    [VO(Sal-L-tryp)(H2O)] 1 (where sal-L-tryp = N-salicylidene-L-tryptophanate) was used as a precursor to produce the novel complexes, [VO(Sal-L-tryp)(MeATSC)].1.5C2H5OH 2 (where MeATSC = 9-Anthraldehyde-N(4)-methylthiosemicarbazone), [VO(Sal-L-tryp)(N-Ethhymethohcarbthio)].H2O 3 (where N-Ethhymethohcarbthio = (E)-N-ethyl-2-(4-hydroxy-3-methoxybenzylidene)hydrazinecarbothioamide), and [VO(Sal-L-tryp)(acetylethTSC)].C2H5OH 4 (where acetylethTSC = (E)-N-ethyl-2-(1-(thiazol-2-yl)ethylidene)hydrazinecarbothioamide), by reaction with the respective thiosemicarbazone. The chemical and structural properties of these ligands and complexes were characterised by elemental analysis, ESI MS, FT-IR, UV-visible, ESR, (1)H and (13)C NMR spectroscopy, and X-ray crystallography. DMSO and DMSO-d6 solutions of compounds 1-4 were oxidised in air to produce vanadium(V) species which were verified by ESI MS and (51)V NMR spectroscopy. Anti-cancer properties of compounds 2-4 were examined with three colon cancer cell lines, HTC-116, Caco-2, and HT-29, and also with non-cancerous colonic myofibroblasts, CCD18-Co. Compounds 2-3 exhibited less inhibitory effects in the CCD-18Co cells, indicating a possible cytotoxic selectivity towards colon cancer cells. In general, those compounds which exhibited anti-proliferative activity on cancer cells, but did not affect non-cancerous cells, may have a potential in chemotherapy.

  19. Design, synthesis and biological evaluation of novel 4-phenoxy-6,7-disubstituted quinolines possessing (thio)semicarbazones as c-Met kinase inhibitors.

    PubMed

    Zhai, Xin; Bao, Guanglong; Wang, Limei; Cheng, Mingke; Zhao, Meng; Zhao, Sijia; Zhou, Hongyang; Gong, Ping

    2016-03-15

    In continuing our efforts to identify small molecules able to inhibit c-Met kinase, three series of novel 6,7-disubstituted-4-phenoxyquinoline derivatives (23a-w, 26a-d and 30a-d) bearing (thio)semicarbazone scaffold were designed, synthesized and evaluated for their cytotoxicity. The biological data revealed that most compounds exhibited moderate-to-excellent activity against HT-29, MKN-45, A549 cancer cell lines and relative poor potency toward MDA-MB-231 cell as well as hardly any cytotoxicity in normal PBL cell. Eleven compounds were further examined for their inhibitory activity against c-Met kinase and three compounds (23h, 23n and 26a) demonstrated good inhibitory activity. This work resulted in the discovery of a potent c-Met inhibitor 23n, bearing 2-hydroxy-3-allylphenyl group at R(2) moiety, as a valuable lead molecule, which possessed remarkable cytotoxicity and high selectivity against A549 and HT-29 cell lines with IC50 values of 11 nM and 27 nM. Besides, it displayed excellent c-Met kinase inhibition on a single-digital nanomolar level (IC50=1.54 nM). Meanwhile, the results from preliminarily in vivo study reflected that compound 23n showed promising overall PK profiles, consistent with the efficacy in both MKN-45 and HT-29 tumor xenograft mice model. These results clearly indicated that compound 23n is a potent and highly selective c-Met inhibitor and its favorable in vitro and in vivo profiles warrant further investigation.

  20. Bis(Dioxolene)(Bipyridine)Ruthenium Redox Series

    DTIC Science & Technology

    1988-07-11

    reactions with isosbestic points were generally observed in these redox processes. The electronic spectra of 02, 01, S, RI and R2 are shown Tor the (1...oOFFICE OF NAVAL RESEARCH Contract NOOOl4-84-G-0201 Task No. 0051-865 Technical Report *23 Bis(Dioxolene)(Bipyridine)Ruthenium Redox Series By...Classit’.’-tion) Bix(Dioxolene)(Bipyridine)Ruthenium Redox Series 12 PERSON4AL AUTHOR(S) A.B. P. Lever*, Pamela R. &uburn, Elaine S. Dodsworth, Masa-A

  1. trans-Bis(hexafluoroantimonato)(phthalocyaninato)copper(II).

    PubMed

    Gardberg, A S; Ibers, J A

    2001-05-01

    The title compound, trans-bis(hexafluoroantimonato-F)(phthalocyaninato-kappa(4)N(29,30,31,32))copper(II), [Cu(SbF(6))(2)(C(32)H(16)N(8))] or Cu(pc)(SbF(6))(2) (pc is phthalocyaninate), comprises a six-coordinate Cu atom, lying on an inversion center, bonded to four N atoms of a phthalocyanine ring and to F atoms of two trans SbF(6)(-) groups. The compound is presumed to consist of a Cu(II) center and a doubly oxidized phthalocyanine ring, by analogy with Cu(pc)(ReO(4))(2).

  2. Polyimide from bis(n-isoprenyl)s of aryl diamides

    NASA Technical Reports Server (NTRS)

    Smith, Joseph G., Jr. (Inventor); Ottenbrite, Raphael M. (Inventor)

    1993-01-01

    A process and polyimide product formed by the reaction of a bismaleimide with a bis(amidediene) is disclosed wherein the bis(amidediene) is formed by reacting an excess of an acid chloride with 1,4-N,N'-diisoprenyl 2,3,5,6-tetramethy1 benzene.

  3. Functional Nanomaterials from Bis-urea Macrocycles

    NASA Astrophysics Data System (ADS)

    Dawn, Sandipan

    Self-assembly of bis-urea macrocycles usually give tubular crystals with nano-sized channels that we use as molecular container. These molecular containers alter the reactivity, stability, and chemical behavior of the reactants entrapped within them. This dissertation is focused on bulk synthesis, material characterization and applications of a self-assembled tubular molecular container. This crystalline straw-like container is developed from cyclic bis-urea macrocycles containing two C-shaped phenylethynylene units and two urea groups. These macrocycles afford a large open channel with a diameter of ˜9 A and it can accommodate larger solid guests such as coumarin and its methylated derivatives, stilbenes, acenaphthylene and styrenes. We developed the method to introduce these solid guests into the channel from its solution. We characterized the tubular host as well as different host*guest complexes by solid-state techniques including PXRD, CP MAS 13C NMR, fluorescence and UV-vis spectroscopy. These guests usually undergo non selective photoreaction in solid-state with very low percent conversion and produce different photodimers and/or isomers. Within our molecular container, a number of guests showed photo-dimerization with amazing selectivity and enhanced conversion in the solid-state. We also performed molecular modeling studies to find out the reason behind this unprecedented selectivity. We found the orientation of the guest molecules inside the channel as well as the stability of the photoproducts within the confinement determines the outcome of the reactions. We also developed a 5,5'-bipyridine containing bis-urea macrocycle and formed its complexes with metals. These complexes have potential to further assemble through dative bonds, hydrogen bonding and aryl stacking interactions to afford metal organic framework (MOF). We found the Ag complex forms oligomers and polymers. In the polymer structure it forms infinite chains comprised of "box" like unit cell

  4. Atomic layer deposition of molybdenum oxide using bis(tert-butylimido)bis(dimethylamido) molybdenum

    SciTech Connect

    Bertuch, Adam Sundaram, Ganesh

    2014-01-15

    Molybdenum trioxide films have been deposited using thermal atomic layer deposition techniques with bis(tert-butylimido)bis(dimethylamido)molybdenum. Films were deposited at temperatures from 100 to 300 °C using ozone as the oxidant for the process. The Mo precursor was evaluated for thermal stability and volatility using thermogravimetric analysis and static vapor pressure measurements. Film properties were evaluated with ellipsometry, x-ray photoelectron spectroscopy, secondary ion mass spectroscopy, and secondary electron microscopy. The growth rate per cycle was determined to extend from 0.3 to 2.4 Å/cycle with <4% nonuniformity (1-sigma) with-in-wafer across a 150 mm wafer for the investigated temperature range.

  5. Evaluation of thiosemicarbazone derivative as chelating agent for the simultaneous removal and trace determination of Cd(II) and Pb(II) in food and water samples.

    PubMed

    Koduru, Janardhan Reddy; Lee, Kap Duk

    2014-05-01

    In the present investigation, prepared N-ethyl-3-carbazolecarbaxaldehyde-3-thiosemicarbazone (ECCT) and employed for the simultaneous removal and determination of trace amounts of Cd(II) and Pb(II) from food and water samples. Cd(II) and Pb(II) gave yellow and orange colored complexes with ECCT in acetate buffer at pH 6.0 with λmax, 380 and 440nm, respectively. Both complexes were easily extractable into kerosene at 1:1(M:L) composition. It was in accordance with Beer's law in the range of 0.0-12.0 and 0.0-10.0μgmL(-1) with 0.999 and 0.997 correlation coefficient for Cd(II) and Pb(II) complexes, respectively, indicated a good linearity between the two variables. The molar absorptivity and Sandell's sensitivity were found to be 0.740×10(4)Lmol(-1)cm(-1), 1.52×10(-3)μgcm(-2) for Cd(II) and 1.809×10(4)L mol(-1)cm(-1), 1.15×10(-3)μgcm(-2) for Pb(II). The precision and accuracy of the method was checked for both metal ions by finding the relative standard deviations (n=8), which were 0.689% and 0.443%, with detection limits of 0.00151μgL(-1) and 0.00264μgL(-1) for Cd(II) and Pb(II), respectively. Further validation using certified reference material, NIST 1568b, resulted in determined concentrations of 0.028±0.253μgg(-1) for Cd(II) and 0.046±0.325μgg(-1) for Pb(II). These determined values agree well with the certified values in the reference materials. The interfering effects of various cations and anions were also studied. The proposed method performance was also evaluated in terms of Student 'T' test and Variance 'F' test, which indicated the significance of the present method parameters, as an inter comparison of the experimental values using ICP-OES.

  6. Bis(4-(3,4-dimethylenepyrrolidyl)-phenyl) methane

    NASA Technical Reports Server (NTRS)

    Ottenbrite, Raphael M. (Inventor)

    1989-01-01

    It is the primary object of the present invention to prepare high temperature polymeric materials, especially linear aromatic polyimides, which maintain their integrity and toughness during long exposure times at elevated temperatures. According to the present invention, this object is achieved, and the attending benefits are obtained, by first providing the bis(exocyclodiene) bis(4-(3,4-dinethylene pyrrolidyl) phenyl) methane, which is formed from the monomer N-phenyl 3,4-dimethylene pyrrolidine. This bis-(exocyclodiene) undergoes Diels-Alder reaction with a bismaleimide without the evolution of gaseous by-products, to form the aromatic polyimide.

  7. Bis (4-(3,4-dimethylene-pyrrolidyl)-phenyl) methane

    NASA Technical Reports Server (NTRS)

    Ottenbrite, Raphael M. (Inventor)

    1990-01-01

    The primary objective is to prepare high temperature polymeric materials, especially linear aromatic polyimides, which maintain their integrity and toughness during long exposure times at elevated temperatures. The attained benefits are obtained by first providing the bis (exocyclodiene) bis (4-(3,4-dimethylene-pyrrolidyl)-phenyl) methane, which is a novel material formed from the monomer N-phenyl-3,4-dimethylene-pyrrolidine. This compound undergoes Diels-Alder reaction with a bismaleimide, without the evolution of gaseous by-products, to form the aromatic polyimide bis (4-(3,4-dimethylene-pyrrolidyl)-phenyl) methane.

  8. Efficient and versatile catalysis of N-alkylation of heterocyclic amines with alcohols and one-pot synthesis of 2-aryl substituted benzazoles with newly designed ruthenium(II) complexes of PNS thiosemicarbazones.

    PubMed

    Ramachandran, Rangasamy; Prakash, Govindan; Selvamurugan, Sellappan; Viswanathamurthi, Periasamy; Malecki, Jan Grzegorz; Ramkumar, Venkatachalam

    2014-06-07

    Ruthenium(II) carbonyl complexes with phosphine-functionalized PNS type thiosemicarbazone ligands [RuCl(CO)(EPh3)(L)] (1-6) (E = P or As, L = 2-(2-(diphenylphosphino)benzylidene) thiosemicarbazone (PNS-H), 2-(2-(diphenylphosphino)benzylidene)-N-methylthiosemicarbazone (PNS-Me), 2-(2-(diphenylphosphino)benzylidene)-N-phenylthiosemicarbazone (PNS-Ph)) have been synthesized and characterized by elemental analysis and spectroscopy (IR, UV-Vis, (1)H, (13)C, (31)P-NMR) as well as ESI mass spectrometry. The molecular structures of complexes 1, 2 and 6 were identified by means of single-crystal X-ray diffraction analysis. The analysis revealed that all the complexes possess a distorted octahedral geometry with the ligand coordinating in a uni-negative tridentate PNS fashion. All the ruthenium complexes (1-6) were tested as catalyst for N-alkylation of heteroaromatic amines with alcohols. Notably, complex 2 was found to be a very efficient and versatile catalyst towards N-alkylation of a wide range of heterocyclic amines with alcohols. Complex 2 can also catalyze the direct amination of 2-nitropyridine with benzyl alcohol to the corresponding secondary amine. Furthermore, a preliminary examination of performance for N,N-dialkylation of diamine showed promising results, giving good conversion and high selectivity. In addition, N-alkylation of ortho-substituted anilines (-NH2, -OH and -SH) led to the one-pot synthesis of 2-aryl substituted benzimidazoles, benzoxazoles and benzothiazoles, also revealing the catalytic activity of complex 2.

  9. 15 CFR Supplement No. 1 to Part 748 - BIS-748P, BIS-748P-A; Item Appendix, and BIS-748P-B; End-User Appendix; Multipurpose Application...

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ..., and BIS-748P-B; End-User Appendix; Multipurpose Application Instructions No. Supplement No. 1 to Part..., BIS-748P-A; Item Appendix, and BIS-748P-B; End-User Appendix; Multipurpose Application Instructions All information must be legibly typed within the lines for each Block or Box, except where a...

  10. Water absorption and transport in bis-silane films.

    PubMed

    Wang, Yimin; Wang, Peng; Kohls, Doug; Hamilton, William A; Schaefer, Dale W

    2009-01-07

    Water (D2O) ingress in bis-amino silane and bis-sulfur silane films was studied by in situ neutron reflectivity. Bis-amino silane film absorbs substantially more D2O (33 vol%) than the bis-sulfur silane film (4.6 vol%) at equilibrium. The volume increase (swelling) of both films, however, is much smaller than the total volume of D2O absorbed in the films. The results suggest that the absorbed water exists in two populations: one is dissolved in the polymer matrix (Henry's mode) while the other occupies unrelaxed free volume existing in the polymer (Langmuir mode). The dominance of Langmuir mode accounts for the small film thickness change during the water absorption. Dual-mode sorption is also consistent with the observed two-stage swelling process whereby an initial rapid increase in film thickness is followed by a slower process extending over 11 h.

  11. Investigation of Zinc bis(1,4-didecylbenzo)-bis(2,3-pyrido) Porphyrazine for Application as Photosensitizer in Photodynamic Therapy of Cancer

    PubMed Central

    Sakamoto, Keiichi; Ohno-Okumura, Eiko; Kato, Taku; Watanabe, Masaki; Cook, Michael J.

    2008-01-01

    The phthalocyanine analogue containing nonperipheral long alkyl-substituted benzenoid rings and pyridine rings, zinc bis(1,4-didecylbenzo)-bis(2,3-pyrido) porphyrazine, was synthesized. Zinc bis(1,4-didecylbenzo)-bis(2,3-pyrido) porphyrazine reacted with dimethyl sulfate and monochloroacetic acid to produce their quaternized products and diethyl sulfate to produce the sulfo-substituted products. All quaternized and sulfo-substituted showed amphiphilic character. Identical peaks in cyclic voltammograms appeared for these products before and after quaternization. During the evaluation of zinc bis(1,4-didecylbenzo)-bis(2,3-pyrido) porphyrazine for its photodynamic therapy of cancer (PDT) efficacy by cancer cell culture, the light exposed dimethyl sulfate quaternized zinc bis(1,4-didecylbenzo)-bis(2,3-pyrido) porphyrazines in IU-002 cells produce cell disruption that can be detected as a decrease in fluorescence. PMID:18350121

  12. Interconnected bis-silylenes: a new dimension in organosilicon chemistry.

    PubMed

    Sen, Sakya S; Khan, Shabana; Nagendran, Selvarajan; Roesky, Herbert W

    2012-04-17

    The past two decades have brought remarkable advances in organosilicon chemistry with the isolation of stable silylenes, persila-allene, and disilynes. The extension of this list gives an impression that it will continue to flourish. The judicous employment of sterically appropriate ligands has enabled the synthesis and isolation of compounds with low-valent silicon. Recently, for example, interconnected bis-silylenes were isolated where the two Si atoms are connected by a σ-bond and each Si atom is possessing a lone pair of electrons. The formal oxidation state of each Si atom in the interconnected bis-silylene is +1, so bis-silylenes can be considered as the valence isomers of disilynes. In this Account, we describe the synthesis of interconnected bis-silylenes and assess their potential as a new building block in organosilicon chemistry. In 2009, we reported the isolation of a bis-silylene ((PhC(NtBu)(2))(2)Si(2)) stabilized by a sterically bulky benz-amidinato ligand with tBu substituents on the nitrogen atoms. Prior to our work, Robinson and co-workers described the synthesis of a N-heterocyclic carbene stabilized bis-silylene. In following years, just two more interconnected bis-silylenes have been reported. Density functional theory calculations to establish the geometric and electronic structures of the reported bis-silylenes have shown that the Wiberg bond index (WBI) for all the reported bis-silylenes is ~1. The synthesis of stable (PhC(NtBu)(2))(2)Si(2) prompted explorations of its reactivity. An important facet of silylene chemistry involves oxidative addition at the Si(II) center with unsaturated substrates, a reaction also available for bis-silylenes. Due to the three reaction sites (two lone pairs of electrons and a labile Si(I)-Si(I) single bond) in the interconnected bis-silylenes, we expect novel product formation. A labile Si-Si bond facilitates the reactions of (PhC(NtBu)(2))(2)Si(2) with diphenyl alkyne or adamantyl phosphaalkyne which

  13. The Structure of Bis(phthalocyaninato)neodymium(III).

    DTIC Science & Technology

    1980-06-01

    synthesis of lanthanide (III) phthalocyanine complexes 1 was established by Kirin and Moskalev, many studies on their composi- 2 tions and properties have...been reported. For instance, intense attention has been directed toward electrochromism of bis(phthalocyaninato) lanthanide (III) complexes , Pc2Ln(III)H...The structural analysis of bis(phthalocyaninato) lanthanide (III) complexes would provide useful information to investigate their electo- chromuism, and

  14. 40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100... Substances § 721.8100 Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis...

  15. 40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100... Substances § 721.8100 Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis...

  16. 40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100... Substances § 721.8100 Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis...

  17. 40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100... Substances § 721.8100 Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis...

  18. 40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100... Substances § 721.8100 Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis...

  19. Surface catalyzed Fenton treatment of bis(2-chloroethyl) ether and bis(2-chloroethoxy) methane.

    PubMed

    Mutuc, Maria D M; Love, Nancy G; Vikesland, Peter J

    2008-02-01

    This study examined the feasibility of using surface catalyzed Fenton treatment to remediate soil and groundwater contaminated by the chlorinated ethers, bis(2-chloroethyl) ether (BCEE) and bis(2-chloroethoxy) methane (BCEM). Parameters that affect the contaminant loss rate such as porewater pH, hydrogen peroxide concentration, and solid/water ratio were systematically evaluated. Batch reactors were set-up utilizing either contaminated or uncontaminated soil, obtained from an industrial site in Moss Point, MS, that was mixed with synthetic groundwater containing the contaminants of interest. The results show an increase in contaminant reduction with a decrease in pH, an increase in hydrogen peroxide concentration, or an increase in the solid/water ratio. For a similar set of conditions, contaminant reduction was greater for systems utilizing contaminated soil as compared to the systems containing uncontaminated soil. In addition, specific oxygen uptake rates (SOURs) were measured for biomass, collected from an activated sludge plant, exposed to different dilutions of untreated and surface catalyzed Fenton treated water to evaluate whether residual BCEE, BCEM, and their co-contaminants as well as their oxidation by-products were potentially inhibitory or can potentially serve as a substrate for the biomass. The measured SOURs show that the surface catalyzed Fenton treatment enhanced the biodegradability of the contaminated groundwater and served as a substrate for the biomass.

  20. Interaction of bis(ethylene)tin(bis(salicylidene)ethylenediamine) with DNA.

    PubMed

    Liu, Guo-Dong; Liao, Jian-Pei; Fang, Yu-Zhi; Huang, Sha-Sheng; Sheng, Guo-Li; Yu, Ru-Qin

    2002-04-01

    The fluorescence spectral characteristics and interaction of bis(ethylene)tin(bis(salicylidene)ethylenediamine) [Et2Sn(salen)] with DNA are described. The polarity of the solvent has a strong effect on the fluorescence characteristics of Et2Sn(salen). Et2Sn(salen) bound to DNA showed a marked decrease in the fluorescence intensity with a bathochromic shift of the excitation and emission peaks. A hypochromism in the UV absorption spectra was also observed. KI quenching and competitive binding to DNA between Et2Sn(salen) and ethidium bromide (EB) were studied in connection with other experimental observations to show that the interactive model between Et2Sn(salen) and DNA is an intercalative one. The pH and salt effect on the fluorescence properties was also investigated. The intrinsic binding constant was estimated to be 1.071 x 10(5) mol L(-1) in base pairs and the binding site number is 1.98, respectively. A linear relationship between F/F0 and the concentration of calf thymus DNA covers 5.1 x 10(-6) - 2.41 x 10(-4) mol L(-1), which can be utilized for determining traces of calf thymus DNA with a detection limit of 1.1 x 10(-7) mol L(-1) in base pairs.

  1. Biochemical characterization of predicted Precambrian RuBisCO

    PubMed Central

    Shih, Patrick M.; Occhialini, Alessandro; Cameron, Jeffrey C.; Andralojc, P John; Parry, Martin A. J.; Kerfeld, Cheryl A.

    2016-01-01

    The antiquity and global abundance of the enzyme, RuBisCO, attests to the crucial and longstanding role it has played in the biogeochemical cycles of Earth over billions of years. The counterproductive oxygenase activity of RuBisCO has persisted over billions of years of evolution, despite its competition with the carboxylase activity necessary for carbon fixation, yet hypotheses regarding the selective pressures governing RuBisCO evolution have been limited to speculation. Here we report the resurrection and biochemical characterization of ancestral RuBisCOs, dating back to over one billion years ago (Gyr ago). Our findings provide an ancient point of reference revealing divergent evolutionary paths taken by eukaryotic homologues towards improved specificity for CO2, versus the evolutionary emphasis on increased rates of carboxylation observed in bacterial homologues. Consistent with these distinctions, in vivo analysis reveals the propensity of ancestral RuBisCO to be encapsulated into modern-day carboxysomes, bacterial organelles central to the cyanobacterial CO2 concentrating mechanism. PMID:26790750

  2. Biochemical characterization of predicted Precambrian RuBisCO.

    PubMed

    Shih, Patrick M; Occhialini, Alessandro; Cameron, Jeffrey C; Andralojc, P John; Parry, Martin A J; Kerfeld, Cheryl A

    2016-01-21

    The antiquity and global abundance of the enzyme, RuBisCO, attests to the crucial and longstanding role it has played in the biogeochemical cycles of Earth over billions of years. The counterproductive oxygenase activity of RuBisCO has persisted over billions of years of evolution, despite its competition with the carboxylase activity necessary for carbon fixation, yet hypotheses regarding the selective pressures governing RuBisCO evolution have been limited to speculation. Here we report the resurrection and biochemical characterization of ancestral RuBisCOs, dating back to over one billion years ago (Gyr ago). Our findings provide an ancient point of reference revealing divergent evolutionary paths taken by eukaryotic homologues towards improved specificity for CO2, versus the evolutionary emphasis on increased rates of carboxylation observed in bacterial homologues. Consistent with these distinctions, in vivo analysis reveals the propensity of ancestral RuBisCO to be encapsulated into modern-day carboxysomes, bacterial organelles central to the cyanobacterial CO2 concentrating mechanism.

  3. Redox-controlled polymerization of lactide catalyzed by bis(imino)pyridine iron bis(alkoxide) complexes.

    PubMed

    Biernesser, Ashley B; Li, Bo; Byers, Jeffery A

    2013-11-06

    Bis(imino)pyridine iron bis(alkoxide) complexes have been synthesized and utilized in the polymerization of (rac)-lactide. The activities of the catalysts were particularly sensitive to the identity of the initiating alkoxide with more electron-donating alkoxides resulting in faster polymerization rates. The reaction displayed characteristics of a living polymerization with production of polymers that exhibited low molecular weight distributions, linear relationships between molecular weight and conversion, and polymer growth observed for up to fifteen sequential additions of lactide monomer to the polymerization reaction. Mechanistic experiments revealed that iron bis(aryloxide) catalysts initiate polymerization with one alkoxide ligand, while iron bis(alkylalkoxide) catalysts initiate polymerization with both alkoxide ligands. Oxidation of an iron(II) catalyst precursor lead to a cationic iron(III) bis-alkoxide complex that was completely inactive toward lactide polymerization. When redox reactions were carried out during lactide polymerization, catalysis could be switched off and turned back on upon oxidation and reduction of the iron catalyst, respectively.

  4. Bis-chalcones and flavones: synthesis and antimicrobial activity.

    PubMed

    Husain, Asif; Rashid, Mohd; Mishra, Ravinesh; Kumar, Deepak

    2013-01-01

    A series of bis-chalcones (3a-g) and their flavones derivatives (4a-g) were synthesized and evaluated for their antimicrobial activity. Bis-chalcones were prepared by condensing 1,1'-(4,6-dihydroxy-1,3-phenylene)diethanone (2) with appropriate aryl aldehydes following Claisen-Schmidt reaction conditions. Oxidative cyclization of bis-chalcones (3a-g) in DMSO in the presence of iodine furnished flavones (4a-g). The synthesized compounds were evaluated for their antibacterial and antifungal actions against some selected microbes. The results of antimicrobial evaluation showed that some of the synthesized compounds were good in their antibacterial and antifungal actions.

  5. Measurement of the fluorescence quantum yield of bis-MSB

    NASA Astrophysics Data System (ADS)

    Ding, Xue-Feng; Wen, Liang-Jian; Zhou, Xiang; Ding, Ya-Yun; Ye, Xing-Chen; Zhou, Li; Liu, Meng-Chao; Cai, Hao; Cao, Jun

    2015-12-01

    The fluorescence quantum yield of bis-MSB, a widely used liquid scintillator wavelength shifter, was measured to study the photon absorption and re-emission processes in a liquid scintillator. The re-emission process affects the photoelectron yield and distribution, especially in a large liquid scintillator detector, thus must be understood to optimize the liquid scintillator for good energy resolution and to precisely simulate the detector with Monte Carlo. In this study, solutions of different bis-MSB concentration were prepared for absorption and fluorescence emission measurements to cover a broad range of wavelengths. Harmane was used as a standard reference to obtain the absolution fluorescence quantum yield. For the first time we measured the fluorescence quantum yield of bis-MSB up to 430 nm as inputs required by Monte Carlo simulation, which is 0.926±0.053 at λex=350 nm. Supported by National Natural Science Foundation of China (11205183, 11225525, 11390381)

  6. 78 FR 8586 - PEPSICO, Inc., Business & Information Solutions (BIS) Division Including On-Site Leased Workers...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-02-06

    ... Employment and Training Administration PEPSICO, Inc., Business & Information Solutions (BIS) Division..., Inc., Business & Information Solutions (BIS) Division Including On-Site Leased Workers From Cognizant Technology Solutions and Infosys Technologies Ltd. Bradenton, FL; Amended Certification Regarding...

  7. Early metal bis(phosphorus-stabilised)carbene chemistry.

    PubMed

    Liddle, Stephen T; Mills, David P; Wooles, Ashley J

    2011-05-01

    Since the discovery of covalently-bound mid- and late-transition metal carbenes there has been a spectacular explosion of interest in their chemistry, but their early metal counterparts have lagged behind. In recent years, bis(phosphorus-stabilised)carbenes have emerged as valuable ligands for metals across the periodic table, and their use has in particular greatly expanded covalently-bound early metal carbene chemistry. In this tutorial review we introduce the reader to bis(phosphorus-stabilised)carbenes, and cover general preparative methods, structure and bonding features, and emerging reactivity studies of early metal derivatives (groups 1-4 and the f-elements).

  8. Di-2-pyridylketone 4,4-dimethyl-3-thiosemicarbazone (Dp44mT) overcomes multidrug resistance by a novel mechanism involving the hijacking of lysosomal P-glycoprotein (Pgp).

    PubMed

    Jansson, Patric J; Yamagishi, Tetsuo; Arvind, Akanksha; Seebacher, Nicole; Gutierrez, Elaine; Stacy, Alexandra; Maleki, Sanaz; Sharp, Danae; Sahni, Sumit; Richardson, Des R

    2015-04-10

    Multidrug resistance (MDR) is a major obstacle in cancer treatment. More than half of human cancers express multidrug-resistant P-glycoprotein (Pgp), which correlates with a poor prognosis. Intriguingly, through an unknown mechanism, some drugs have greater activity in drug-resistant tumor cells than their drug-sensitive counterparts. Herein, we investigate how the novel anti-tumor agent di-2-pyridylketone 4,4-dimethyl-3-thiosemicarbazone (Dp44mT) overcomes MDR. Four different cell types were utilized to evaluate the effect of Pgp-potentiated lysosomal targeting of drugs to overcome MDR. To assess the mechanism of how Dp44mT overcomes drug resistance, cellular studies utilized Pgp inhibitors, Pgp silencing, lysosomotropic agents, proliferation assays, immunoblotting, a Pgp-ATPase activity assay, radiolabeled drug uptake/efflux, a rhodamine 123 retention assay, lysosomal membrane permeability assessment, and DCF (2',7'-dichlorofluorescin) redox studies. Anti-tumor activity and selectivity of Dp44mT in Pgp-expressing, MDR cells versus drug-sensitive cells were studied using a BALB/c nu/nu xenograft mouse model. We demonstrate that Dp44mT is transported by the lysosomal Pgp drug pump, causing lysosomal targeting of Dp44mT and resulting in enhanced cytotoxicity in MDR cells. Lysosomal Pgp and pH were shown to be crucial for increasing Dp44mT-mediated lysosomal damage and subsequent cytotoxicity in drug-resistant cells, with Dp44mT being demonstrated to be a Pgp substrate. Indeed, Pgp-dependent lysosomal damage and cytotoxicity of Dp44mT were abrogated by Pgp inhibitors, Pgp silencing, or increasing lysosomal pH using lysosomotropic bases. In vivo, Dp44mT potently targeted chemotherapy-resistant human Pgp-expressing xenografted tumors relative to non-Pgp-expressing tumors in mice. This study highlights a novel Pgp hijacking strategy of the unique dipyridylthiosemicarbazone series of thiosemicarbazones that overcome MDR via utilization of lysosomal Pgp transport activity.

  9. 40 CFR 721.10096 - Benzene, 1,4-bis (methoxymethyl)-.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Benzene, 1,4-bis (methoxymethyl)-. 721... Substances § 721.10096 Benzene, 1,4-bis (methoxymethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 1,4-bis (methoxymethyl)- (PMN...

  10. 40 CFR 721.10096 - Benzene, 1,4-bis (methoxymethyl)-.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Benzene, 1,4-bis (methoxymethyl)-. 721... Substances § 721.10096 Benzene, 1,4-bis (methoxymethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 1,4-bis (methoxymethyl)- (PMN...

  11. 40 CFR 721.10096 - Benzene, 1,4-bis (methoxymethyl)-.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Benzene, 1,4-bis (methoxymethyl)-. 721... Substances § 721.10096 Benzene, 1,4-bis (methoxymethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 1,4-bis (methoxymethyl)- (PMN...

  12. 40 CFR 721.10096 - Benzene, 1,4-bis (methoxymethyl)-.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Benzene, 1,4-bis (methoxymethyl)-. 721... Substances § 721.10096 Benzene, 1,4-bis (methoxymethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 1,4-bis (methoxymethyl)- (PMN...

  13. 40 CFR 721.10096 - Benzene, 1,4-bis (methoxymethyl)-.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Benzene, 1,4-bis (methoxymethyl)-. 721... Substances § 721.10096 Benzene, 1,4-bis (methoxymethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 1,4-bis (methoxymethyl)- (PMN...

  14. Regioselective preparation of a bis-pyrazolinofullerene by a macrocyclization reaction.

    PubMed

    Cuesta, Virginia; Urbani, Maxence; de la Cruz, Pilar; Welte, Lorena; Nierengarten, Jean-François; Langa, Fernando

    2016-11-03

    A single isomer of a pyrazolinofullerene bis-adduct was prepared by tether-directed remote functionalization. Specifically, a macrocyclization reaction between C60 and a bis-hydrazone reagent has been carried out to generate a regioisomerically pure fullerene bis-adduct which presents a lower LUMO than pristine C60.

  15. A facile route to aromatic ring-annelated bis(ethylenedithio) tretrathiafluvalene derivatives

    SciTech Connect

    Parakka, J.P.; Kini, A.M.; Williams, J.M.

    1996-12-31

    The synthesis of bis(benzo)- and bis(naphtho)-fused derivatives of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) is easily achieved by employing the (4+2) cycloaddition reaction of oligo(1,3-dithiole-2,4,5-trithione) with appropriate olefins as the key step.

  16. 40 CFR 721.3340 - Ethanol, 2,2′-(hexylamino)bis-.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Ethanol, 2,2â²-(hexylamino)bis-. 721... Substances § 721.3340 Ethanol, 2,2′-(hexylamino)bis-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-(hexylamino)bis- (PMN...

  17. 40 CFR 721.3340 - Ethanol, 2,2′-(hexylamino)bis-.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethanol, 2,2â²-(hexylamino)bis-. 721... Substances § 721.3340 Ethanol, 2,2′-(hexylamino)bis-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-(hexylamino)bis- (PMN...

  18. 40 CFR 721.3340 - Ethanol, 2,2′-(hexylamino)bis-.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Ethanol, 2,2â²-(hexylamino)bis-. 721... Substances § 721.3340 Ethanol, 2,2′-(hexylamino)bis-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-(hexylamino)bis- (PMN...

  19. 40 CFR 721.3340 - Ethanol, 2,2′-(hexylamino)bis-.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Ethanol, 2,2â²-(hexylamino)bis-. 721... Substances § 721.3340 Ethanol, 2,2′-(hexylamino)bis-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-(hexylamino)bis- (PMN...

  20. 40 CFR 721.3340 - Ethanol, 2,2′-(hexylamino)bis-.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Ethanol, 2,2â²-(hexylamino)bis-. 721... Substances § 721.3340 Ethanol, 2,2′-(hexylamino)bis-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-(hexylamino)bis- (PMN...

  1. The triazine-based azo-azomethine dyes; synthesis, characterization, spectroscopy, solvatochromism and biological properties of 2,2'-(((6-methoxy-1,3,5-triazine-2,4-diyl)bis(sulfanediyl)bis(2,1-phenylene))bis(azanylylidene)bis(methanylylidene))bis(4-(phenyldiazenyl)phenol).

    PubMed

    Ghasemian, Motaleb; Kakanejadifard, Ali; Azarbani, Farideh; Zabardasti, Abedin; Shirali, Somayeh; Saki, Zeinab; Kakanejadifard, Sahar

    2015-03-05

    The macrocyclic azo-azomethine dyes 2,2'-(((6-methoxy-1,3,5-triazine-2,4-diyl)bis(sulfanediyl)bis(2,1-phenylene))bis(azanylylidene)bis(methanylylidene))bis(4-(phenyldiazenyl)phenol) and its derivatives were synthesized and characterized by elemental analysis, mass, FT-IR, UV-vis and NMR spectroscopy. The solvatochromism as well as effects of substitutions on the electronic absorption of these compounds have been studied in the DMSO, DMF, THF, CH3CN, CH3OH and CH3COOH as solvents. Also they positive solvatochromism behaviors are explained on the basis of intramolecular hydrogen bonding, enol-keto tautomeric and dipole moment changes. Compounds having electron donating substituent on the phenyl ring showed good antioxidant activity. However, none of them has a considerable antibacterial activity.

  2. The triazine-based azo-azomethine dyes; synthesis, characterization, spectroscopy, solvatochromism and biological properties of 2,2‧-(((6-methoxy-1,3,5-triazine-2,4-diyl)bis(sulfanediyl)bis(2,1-phenylene))bis(azanylylidene)bis(methanylylidene))bis(4-(phenyldiazenyl)phenol)

    NASA Astrophysics Data System (ADS)

    Ghasemian, Motaleb; Kakanejadifard, Ali; Azarbani, Farideh; Zabardasti, Abedin; Shirali, Somayeh; Saki, Zeinab; Kakanejadifard, Sahar

    2015-03-01

    The macrocyclic azo-azomethine dyes 2,2‧-(((6-methoxy-1,3,5-triazine-2,4-diyl)bis(sulfanediyl)bis(2,1-phenylene))bis(azanylylidene)bis(methanylylidene))bis(4-(phenyldiazenyl)phenol) and its derivatives were synthesized and characterized by elemental analysis, mass, FT-IR, UV-vis and NMR spectroscopy. The solvatochromism as well as effects of substitutions on the electronic absorption of these compounds have been studied in the DMSO, DMF, THF, CH3CN, CH3OH and CH3COOH as solvents. Also they positive solvatochromism behaviors are explained on the basis of intramolecular hydrogen bonding, enol-keto tautomeric and dipole moment changes. Compounds having electron donating substituent on the phenyl ring showed good antioxidant activity. However, none of them has a considerable antibacterial activity.

  3. Poly[bis-(acetonitrile-κN)bis-[μ(3)-bis(tri-fluoro-methane-sulfonyl)-imido-κO,O':O'':O''']dilithium].

    PubMed

    Seo, Daniel M; Boyle, Paul D; Henderson, Wesley A

    2011-05-01

    In the title compound, [Li(2)(CF(3)SO(2)NSO(2)CF(3))(2)(CH(3)CN)(2)](n), two Li(+) cations reside on crystallographic inversion centers, each coordinated by six O atoms from bis(trifluoromethanesulfonyl)imide (TFSI(-)) anions. The third Li(+) cation on a general position is four-coordinated by two anion O atoms and two N atoms from acetonitrile mol-ecules in a tetra-hedral geometry.

  4. Rhodium complexes bearing tetradentate diamine-bis(phenolate) ligands

    SciTech Connect

    Liu, Xiang Y; Lokare, Kapil S; Ganesh, Somesh K; Gonzales, Jason M; Oxgaard, Jonas; Goddard, William A; Periana, Roy A

    2011-01-01

    Using tetradentate, dianionic ligands, several new rhodium complexes have been prepared. Some of these diamine-bis(phenolate) compounds, are active for C–H activation of benzene. These complexes are air and thermally stable. All four complexes were characterized by X-ray diffraction.

  5. Glucose selective bis-boronic acid click-fluor.

    PubMed

    Zhai, Wenlei; Male, Louise; Fossey, John S

    2017-02-14

    Four novel bis-boronic acid compounds were synthesised via copper catalysed azide-alkyne cycloaddition (CuAAC) reactions. Glucose selectivity was observed for a particular structural motif. Moreover, a new glucose selective fluorescent sensor was designed and synthesised as a result.

  6. 29 CFR 1915.1008 - bis-Chloromethyl ether.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 7 2010-07-01 2010-07-01 false bis-Chloromethyl ether. 1915.1008 Section 1915.1008 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR (CONTINUED) OCCUPATIONAL SAFETY AND HEALTH STANDARDS FOR SHIPYARD EMPLOYMENT Toxic and Hazardous...

  7. Hydrolytic and aminolytic kinetic resolution of terminal bis-epoxides.

    PubMed

    Bredihhina, Jevgenia; Villo, Piret; Andersons, Kārlis; Toom, Lauri; Vares, Lauri

    2013-03-15

    Hydrolytic and aminolytic kinetic resolution of terminal bis-epoxides catalyzed by (salen)Co(III) complexes affords epoxy-diols and N-protected epoxy-amino alcohols with excellent enantio- and diastereoselectivity and good yields. An operationally simple procedure gives instant access to valuable building blocks containing two remote stereocenters in highly enantioenriched form.

  8. Combinatorial Libraries of Bis-Heterocyclic Compounds with Skeletal Diversity

    PubMed Central

    Soural, Miroslav; Bouillon, Isabelle; Krchňák, Viktor

    2009-01-01

    Combinatorial solid-phase synthesis of bis-heterocyclic compounds, characterized by the presence of two heterocyclic cores connected by a spacer of variable length/structure, provided structurally heterogeneous libraries with skeletal diversity. Both heterocyclic rings were assembled on resin in a combinatorial fashion. PMID:18811208

  9. Diastereoselective Synthesis of Diketopiperazine Bis-α,β-Epoxides

    PubMed Central

    Ando, Shin; Grote, Amy L.; Koide, Kazunori

    2011-01-01

    Functionalized diketopiperazines (a.k.a. dioxopiperazines) are an important class of molecules in medicinal chemistry and material science. Herein we report a diastereoselective synthesis of diketopiperazine bis-α,β-epoxides via the oxidation of exocyclic olefins. Although six diastereomers may be formed by this approach, only one or two of them were observed. PMID:21250704

  10. 4,4\\'-Methylene bis(N,N\\'-dimethyl)aniline

    Integrated Risk Information System (IRIS)

    4,4 ' - Methylene bis ( N , N ' - dimethyl ) aniline ; CASRN 101 - 61 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Haz

  11. Synthesis and Characterization of Novel Cu(II), Pd(II) and Pt(II) Complexes with 8-Ethyl-2-hydroxytricyclo(7.3.1.0(2,7))tridecan-13-one-thiosemicarbazone: Antimicrobial and in Vitro Antiproliferative Activity.

    PubMed

    Pahonțu, Elena; Paraschivescu, Codruța; Ilieș, Diana-Carolina; Poirier, Donald; Oprean, Camelia; Păunescu, Virgil; Gulea, Aurelian; Roșu, Tudor; Bratu, Ovidiu

    2016-05-21

    New Cu(II), Pd(II) and Pt(II) complexes, (Cu(L)(H₂O)₂(OAc)) (1), (Cu(HL)(H₂O)₂(SO₄)) (2), (Cu(L)(H₂O)₂(NO₃)) (3), (Cu(L)(H₂O)₂(ClO₄)) (4), (Cu(L)₂(H₂O)₂) (5), (Pd(L)(OAc))H₂O (6), and (Pt(L)₂) (7) were synthesized from 8-ethyl-2-hydroxytricyclo(7.3.1.0(2,7))tridecan-13-one thiosemicarbazone (HL). The ligand and its metal complexes were characterized by IR, ¹H-NMR, (13)C-NMR, UV-Vis, FAB, EPR, mass spectroscopy, elemental and thermal analysis, magnetic susceptibility measurements and molar electric conductivity. The free ligand and the metal complexes have been tested for their antimicrobial activity against E. coli, S. enteritidis, S. aureus, E. faecalis, C. albicans and cytotoxicity against the NCI-H1573 lung adenocarcinoma, SKBR-3 human breast, MCF-7 human breast, A375 human melanoma and HL-60 human promyelocytic leukemia cell lines. Copper complex 2 exhibited the best antiproliferative activities against MCF-7 human breast cancer cells. A significant inhibition of malignant HL-60 cell growth was observed for copper complex 2, palladium complex 6 and platinum complex 7, with IC50 values of 1.6 µM, 6.5 µM and 6.4 µM, respectively.

  12. 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.

    PubMed

    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.

  13. Mn(II), Co(II), Zn(II), Fe(III) and U (VI) complexes of 2-acetylpyridine 4N-(2-pyridyl) thiosemicarbazone (HAPT); structural, spectroscopic and biological studies

    NASA Astrophysics Data System (ADS)

    El-Ayaan, Usama; Youssef, Magdy M.; Al-Shihry, Shar

    2009-11-01

    The present work carried out a study on transition metal ion complexes which have been synthesized from 2-acetylpyridine 4N-(2-pyridyl) thiosemicarbazone (HAPT) 1. These complexes namely [Zn(HAPT)Cl 2] 2, [Mn (HAPT)Cl 2] 3, [Co (HAPT)Cl 2] 4, [Fe(APT)Cl 2(H 2O)] 5 and [UO 2(HAPT)(OAc) 2] 6, were characterized by elemental analysis, spectral (IR, 1H NMR and UV-vis) and magnetic moment measurements. Thermal properties and decomposition kinetics of all compounds are investigated. The interpretation, mathematical analysis and evaluation of kinetic parameters ( E, A, Δ H, Δ S and Δ G) of all thermal decomposition stages have been evaluated using Coats-Redfern equation. The biochemical studies showed that, complexes 3 and 6 have powerful and complete degradation effect on the both DNA and protein. The SOD-like activity exhibited that complex 3 has a strong antioxidative properties. The antibacterial screening demonstrated that, the free ligand (HAPT), complexes 2, 3 and 6 have the maximum and broad activities against Gram-positive and Gram-negative bacterial strains.

  14. Thermal behavior of poly(2-hydroxyethyl methacrylate-bis-[trimethoxysilylpropyl]amine) networks

    NASA Astrophysics Data System (ADS)

    Bustos Figueroa, L. A.; Salgado Delgado, R.; García Hernandez, E.; Vargas Galarza, Z.; Rubio Rosas, E.; Salgado Rodriguez, R.

    2013-06-01

    Poly(HEMA-BisSi) networks were prepared by using acid-catalyzed sol-gel of bis-[trimethoxysilylpropyl]amine (BisSi) and free radical polymerization of 2-hydroxyethyl methacrylate (HEMA). The thermal properties of the poly(HEMA-BisSi) networks were investigated with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The thermal behavior of these networks was also compared with homopolymers (The networks formed in both PHEMA and PBisSi gels were identified). The glass transition temperature (Tg) of PHEMA homopolymer was found as 103.74 °C. The thermal degradation of the poly(HEMA-BisSi) networks with different silica contents (e.g. 10, 15 and 25 wt%) were evaluated with use of DTG. It was observed that the thermal degradation temperature of poly(HEMA-BisSi) networks changed much with the BisSi content.

  15. μ-Carbonato-bis­(bis­{2-[(diethyl­amino)­meth­yl]phen­yl}bis­muth(III))

    PubMed Central

    Soran, Albert P.; Nema, Mihai G.; Breunig, Hans J.; Silvestru, Cristian

    2011-01-01

    The mol­ecular structure of the title compound, [Bi2(C11H16N)4(CO3)], consists of a symmetrically bridging carbonato group which binds two [2-Et2NCH2C6H4]2Bi units that are crystallographically related via a twofold rotation axis bis­ecting the carbonate group. The two Bi atoms and two of the C atoms directly bonded to bis­muth are quasi-planar [deviations of 0.323 (1) and 0.330 (9)Å for the Bi and C atoms, respectively] with the carbonate group. The remaining two ligands are in a trans arrangement relative to the quasi-planar (CBi)2CO3 system. The metal atom is strongly coordinated by the N atom of one pendant arm [Bi—N = 2.739 (6) Å], almost trans to the O atom, while the N atom of the other pendant arm exhibits a weaker intra­molecular inter­action [Bi⋯N = 3.659 (7) Å] almost trans to a C atom. If both these intra­molecular N→Bi inter­actions per metal atom are considered, the overall coordination geometry at bis­muth becomes distorted square-pyramidal [(C,N)2BiO cores] and the compound can be described as a hypervalent 12-Bi-5 species. Additional quite short intra­molecular Bi⋯O inter­actions are also present [3.796 (8)–4.020 (9) Å]. Inter­molecular associations through weak η6⋯Bi inter­actions [Bi⋯centroid of benzene ring = 3.659 (1) Å] lead to a ribbon-like supra­molecular association. PMID:21522836

  16. Asymmetric Michael addition of nitroalkanes to nitroalkenes catalyzed by C2-symmetric tridentate bis(oxazoline) and bis(thiazoline) zinc complexes.

    PubMed

    Lu, Shao-Feng; Du, Da-Ming; Xu, Jiaxi; Zhang, Shi-Wei

    2006-06-14

    The first asymmetric synthesis of 1,3-dinitro compounds through Michael addition of nitroalkanes to nitroalkenes catalyzed by C2-symmetric chiral tridentate bis(oxazoline) and bis(thiazoline) zinc complexes was achieved with high enantioselectivities (up to 95% ee).

  17. 21 CFR 73.3100 - 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedione bis(2-propenoic)ester copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false 1,4-Bis -9,10-anthracenedione bis(2-propenoic)ester copolymers. 73.3100 Section 73.3100 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF... intended coloring effect. (2) Authorization and compliance with these uses shall not be construed...

  18. Microwave assisted synthesis of bis and tris(ω-bromoacetophenones): versatile precursors for novel bis(imidazo[1,2-a]pyridines), bis(imidazo[1,2-a]pyrimidines) and their tris-analogs

    PubMed Central

    2013-01-01

    Background α-Bromination of the side chain of aromatic ketones using NBS in the presence of p-toluenesulfonic acid (p-TsOH) in acetonitrile is very common. However, regioselective bromination of bis and tris(ω-bromoacetophenones) with NBS in the presence of p-TsOH in acetonitrile under microwave irradiation is quite novel. The bis- and tris(ω-bromoacetophenones) are used in synthesis of bis and tris(heterocycles). bis(heterocycles) have received a great deal of attention, because many biologically active natural and synthetic products have molecular symmetry. The use of the pressurized microwave irradiation is very advantageous to many syntheses and provide a large rate enhancement. Results Bis and tris(ω-bromoacetophenones) were obtained as single monobrominated derivatives in a shorter time than the conventional conditions. The results clearly demonstrate the better reactivity and selectivity of NBS/p-TsOH/CH3CN as a brominating mixture under microwave conditions. The reaction of bis and tris(ω-bromoacetophenone) with 2-aminopyridine and 2-aminopyrimidine proceeded smoothly in a mixture of anhydrous ethanol and DMF under reflux or using 300 W/105°C/ 20 min microwave irradiation conditions to afford the corresponding bis(imidazo[1,2-a]pyridine), bis(imidazo[1,2-a]pyrimidine) and tris(imidazo[1,2-a]pyridine) derivatives in moderate to excellent yields. The carbonyl analogue of the targeted bis(imidazopyridines) could be synthesized by the reaction of N,N-dimethyl-N'-(pyridin-2-yl)formimidamide with bis(ω-bromoacetophenone) in refluxing ethanol. The structures of the newly synthesized compounds were confirmed by their spectral data as well as their elemental analyses. Conclusion In conclusion, selective α-bromination of bis- and tris(acetophenones) has been accomplished efficiently utilizing NBS/p-TsOH/CH3CN under microwave irradiation. In addition, a facile synthesis of novel series of bis- and tris(imidazopyridine) and bis(imidazopyrimidine) derivatives

  19. Superconductivity in layered BiS2-based compounds

    DOE PAGES

    Yazici, D.; Jeon, I.; White, B. D.; ...

    2015-02-25

    Here, a novel family of superconductors based on BiS2-based superconducting layers were discovered in 2012. In short order, other BiS2-based superconductors with the same or related crystal structures were discovered with superconducting critical temperatures Tc of up to 10 K. Many experimental and theoretical studies have been carried out with the goal of establishing the basic properties of these new materials and understanding the underlying mechanism for superconductivity. In this selective review of the literature, we distill the central discoveries from this extensive body of work, and discuss the results from different types of experiments on these materials within themore » context of theoretical concepts and models.« less

  20. [1,3-Bis(diphenylphosphino)propane]trichlorooxorhenium(V).

    PubMed

    Suescun, L; Mombrú, A W; Mariezcurrena, R A; Pardo, H; Russi, S; Kremer, C; Rivero, M; Kremer, E

    2000-08-01

    Trichlorooxo[1,3-propanediylbis(diphenylphosphine)-P,P ']rhenium(V), [ReCl(3)O(C(27)H(26)P(2))], crystallizes with four formula units per unit cell. The crystal structure consists of neutral complexes of [ReOCl(3)(dppp)] [dppp is 1,3-bis(diphenylphosphino)propane] packed by H.pi-ring interactions. The Re atom is octahedrally coordinated to the oxo anion, three Cl atoms and two P atoms from the dppp ligand. The six-membered ring formed by the bidentate dppp ligand and the rhenium metal centre is in a chair conformation. The title compound is an intermediate in the synthesis of bis(dppp) complexes of rhenium.

  1. Synthesis and Characterization of bis(Tetrahydrofurfuryl) Ether

    PubMed Central

    Stenger‐Smith, John D.; Baldwin, Lawrence; Chafin, Andrew

    2016-01-01

    Abstract Despite the availability of a large number of alkyl tetrahydrofurfuryl ethers that have a wide range of applications, pure bis(tetrahydrofurfuryl) ether (BTHFE) has not been previously synthesized. Here, we report the synthesis of BTHFE (consisting of the RR, SS, and meso stereoisomers) at greater than 99 % purity from tetrahydrofurfuryl alcohol, using (tetrahydrofuran‐2‐yl)methyl methanesulfonate as an intermediate. Additionally, we demonstrate that BTHFE can be used as a non‐volatile solvent in poly(3,4‐propylenedioxythiophene)‐based supercapacitors. Supercapacitor devices employing solutions of the ionic liquid 1‐ethyl‐3‐methyl‐imidizolium bis(trifluoromethylsulfonyl)imide in BTHFE display similar performances to those prepared by using the neat ionic liquid as an electrolyte, although solution‐based devices exhibit a somewhat higher resistance. PMID:27547636

  2. Method for synthesizing metal bis(borano) hypophosphite complexes

    DOEpatents

    Cordaro, Joseph G.

    2013-06-18

    The present invention describes the synthesis of a family of metal bis(borano) hypophosphite complexes. One procedure described in detail is the syntheses of complexes beginning from phosphorus trichloride and sodium borohydride. Temperature, solvent, concentration, and atmosphere are all critical to ensure product formation. In the case of sodium bis(borano) hypophosphite, hydrogen gas was evolved upon heating at temperatures above 150.degree. C. Included in this family of materials are the salts of the alkali metals Li, Na and K, and those of the alkaline earth metals Mg and Ca. Hydrogen storage materials are possible. In particular the lithium salt, Li[PH.sub.2(BH.sub.3).sub.2], theoretically would contain nearly 12 wt % hydrogen. Analytical data for product characterization and thermal properties are given.

  3. Synthesis and structure of triphenylbismuth bis(3-phenylprop-2-enoate)

    SciTech Connect

    Andreev, P. V. Somov, N. V.; Kalistratova, O. S.; Gushchin, A. V.; Chuprunov, E. V.

    2015-07-15

    The newly synthesized triphenylbismuth bis(3-phenylprop-2-enoate) was studied by X-ray diffraction and by IR, UV, and NMR spectroscopy. The crystals are monoclinic, sp. gr. C2/c, Z = 4, a = 13.2820(4) Å, b = 21.3750(2) Å, c = 12.2407(2) Å, β = 119.936(1)°. The coordination polyhedron of the bismuth atom can be described as a distorted pentagonal bipyramid.

  4. Synthesis and Structure of a Novel Bis-Stibole

    DTIC Science & Technology

    1994-10-18

    are thermochromic . 3 in this account, we report the synthesis and solid state structure of some unusual bis- stibolobenzene dervatives. We have... material through the column. The solvent was removed In vacuo to leave a yellow solid (0.265 g, 0.434 mreol, 71%). This material was dissolved in...from the remaining material by fractional crystallization were unsuccessful. In a separate experiment, a mixture of 2a and 2b was crystallized from

  5. Bis(vinylenedithio)tetrathiafulvalene analogues of BEDT-TTF

    PubMed Central

    Demirtas, İlknur; Ozturk, Turan

    2015-01-01

    Summary This review aims to give an overview of the current status of our research on the synthesis of π-electron donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF, ET) analogues prepared from 1,8-diketones via a ring forming reaction. The new synthesized π-electron donors have vinyl moieties producing extended π-electron delocalization over the substituent phenyl rings at the peripheries. PMID:25977714

  6. [N,N-Bis(diphenyl-phosphino)isopropyl-amine]dibromidonickel(II).

    PubMed

    Hapke, Marko; Wöhl, Anina; Peitz, Stephan; Müller, Bernd H; Spannenberg, Anke; Rosenthal, Uwe

    2009-02-06

    The title compound, [NiBr(2)(C(27)H(27)NP(2))], was synthesized by the reaction of NiBr(2)(dme) (dme is 1,2-dimethoxy-ethane) with N,N-bis-(diphenyl-phosphino)isopropyl-amine in methanol/tetra-hydro-furan. The nickel(II) center is coordinated by two P atoms of the chelating PNP ligand, Ph(2)PN(iPr)PPh(2), and two bromide ions in a distorted square-planar geometry.

  7. Synthesis of N- and S-bis-protected lactosyl isothiobiurets.

    PubMed

    Dandale, Anvita S; Mangte, Dattatraya V; Deshmukh, Shirish P

    2007-04-09

    Several N,S-bis(hepta-O-acetyllactosyl)-1-aryl-2-isothiobiuret compounds have been synthesised for the first time by the reaction of S-(hepta-O-acetyl-beta-lactosyl)-1-arylisothiocarbamides and hepta-O-acetyl-beta-lactosyl isocyanate. The identities of these newly synthesised compounds were established on the basis of elemental analysis and IR, (1)H NMR, (13)C NMR and mass spectral studies.

  8. catena-Poly[[[di­aqua­bis­[1,2-bis­(pyridin-4-yl)diazene]copper(II)]-μ-1,2-bis­(pyridin-4-yl)diazene] bis­(perchlorate)

    PubMed Central

    Ballestero-Martínez, Ernesto; Campos-Fernández, Cristian Saul; Soto-Tellini, Victor Hugo; Gonzalez-Montiel, Simplicio; Martínez-Otero, Diego

    2013-01-01

    In the title compound, {[Cu(C10H8N4)3(H2O)2](ClO4)2}n, the coordination environment of the cationic CuII atom is distorted octa­hedral, formed by pairs of symmetry-equivalent 1,2-bis­(pyridin-4-yl)diazene ligands, bridging 1,2-bis­(pyridin-4-yl)diazene ligands and two non-equivalent water mol­ecules. The 1,2-bis­(pyridin-4-yl)diazene mol­ecules form polymeric chains parallel to [-101] via azo bonds which are situated about inversion centres. Since the CuII atom is situated on a twofold rotation axis, the monomeric unit has point symmetry 2. The perchlorate anions are disordered in a 0.536 (9):0.464 (9) ratio and are acceptors of water H atoms in medium–strong O—H⋯O hydrogen bonds with graph set R 4 4(12). The water mol­ecules, which are coordinated to the CuII atom and are hydrogen-bonded to the perchlorate anions, form columns parallel to [010]. A π–π inter­action [centroid–centroid distance = 3.913 (2) Å] occurs between pyridine rings, and weak C—H⋯O inter­actions also occur. PMID:23794983

  9. catena-Poly[[[di-aqua-bis-[1,2-bis-(pyridin-4-yl)diazene]copper(II)]-μ-1,2-bis-(pyridin-4-yl)diazene] bis-(perchlorate)].

    PubMed

    Ballestero-Martínez, Ernesto; Campos-Fernández, Cristian Saul; Soto-Tellini, Victor Hugo; Gonzalez-Montiel, Simplicio; Martínez-Otero, Diego

    2013-06-01

    In the title compound, {[Cu(C10H8N4)3(H2O)2](ClO4)2} n , the coordination environment of the cationic Cu(II) atom is distorted octa-hedral, formed by pairs of symmetry-equivalent 1,2-bis-(pyridin-4-yl)diazene ligands, bridging 1,2-bis-(pyridin-4-yl)diazene ligands and two non-equivalent water mol-ecules. The 1,2-bis-(pyridin-4-yl)diazene mol-ecules form polymeric chains parallel to [-101] via azo bonds which are situated about inversion centres. Since the Cu(II) atom is situated on a twofold rotation axis, the monomeric unit has point symmetry 2. The perchlorate anions are disordered in a 0.536 (9):0.464 (9) ratio and are acceptors of water H atoms in medium-strong O-H⋯O hydrogen bonds with graph set R 4 (4)(12). The water mol-ecules, which are coordinated to the Cu(II) atom and are hydrogen-bonded to the perchlorate anions, form columns parallel to [010]. A π-π inter-action [centroid-centroid distance = 3.913 (2) Å] occurs between pyridine rings, and weak C-H⋯O inter-actions also occur.

  10. X-ray diffraction and vibrational spectroscopic study of trans-bis(acetylacetonato)-bis(4-methylpyridine)cobalt(III)

    NASA Astrophysics Data System (ADS)

    Tayyari, Sayyed Faramarz; Habibi, Mohammad Hossien; Shojaee, Elahe; Jamialahmadi, Mina; Sammelson, Robert Erik; Wada, Koki; Suzuki, Takayoshi

    2015-03-01

    Trans-bis(acetylacetonato)-bis(4-methylpyridine)cobalt(III)hexafluorophosphate, [AMPC]PF6, was synthesized and characterized by X-ray diffraction and vibrational spectroscopy. The title compound C22H28N2O4Co crystallizes with Z = 2 in space group P-1 (#2). The molecular structure and vibrational spectra of this compound were investigated by means of density functional theory (DFT) calculations and the results were compared with the experimental data. The measured IR bands were interpreted in terms of the calculated vibrational normal modes and compared with the tris(acetylacetonate)Co(III) (Co(acac)3) and 4-methylpyridine (4-Mepy) vibrational spectra. The scaled theoretical wavenumbers and the structural parameters were in excellent agreement with the experimental data.

  11. Synthesis and evaluation of in vivo antioxidant, in vitro antibacterial, MRSA and antifungal activity of novel substituted isatin N-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)thiosemicarbazones.

    PubMed

    Thanh, Nguyen Dinh; Giang, Nguyen Thi Kim; Quyen, Tran Ha; Huong, Doan Thi; Toan, Vu Ngoc

    2016-11-10

    Some new isatin N-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)thiosemicarbazones 4a-t with different substituents at 1-, 5- and 7-positions of isatin ring have been synthesized by reaction of N-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)thiosemicarbazide 2 with corresponding isatins 3a-t. Compounds 4a-t were evaluated in vivo for antioxidant activity and in vitro for anti-microorganism activities. The MIC values were found for Gram positive bacteria (MIC = 1.56-6.25 μM), for Gram negative bacteria (MIC = 12.5 μM), and for fungi Aspergillus niger (MIC = 3.12-12.5 μM), Fusarium oxysporum (MIC = 6.25-12.5 μM) and Saccharomyces cerevisiae (MIC = 6.25-12.5 μM). Regarding the antioxidant activity, the SOD, GHS-Px and catalase activities of 4c-i and 4m-r were MIC = 10.57-10.85, 0.27-0.93 and 345.45-399.75 unit/mg protein, respectively. Compounds 4e-h had MIC values of 0.78, 1.56, and 3.12 μM for three clinical MRSA isolates. Compound 4e showed the selective cytotoxic effects against some cancer (LU-1, HepG2, MCF7, P338, SW480, KB) cell lines and normal fibroblast cell line NIH/3T3.

  12. Synthesis, characterization antibacterial and antiproliferative activity of novel Cu(II) and Pd(II) complexes with 2-hydroxy-8-R-tricyclo[7.3.1.0.(2,7)]tridecane-13-one thiosemicarbazone.

    PubMed

    Rosu, Tudor; Pahontu, Elena; Pasculescu, Simona; Georgescu, Rodica; Stanica, Nicolae; Curaj, Adelina; Popescu, Alexandra; Leabu, Mircea

    2010-04-01

    Synthesis and biological activity investigation of complex compounds of Cu(II) are challenging issues because of the metal is not a xenobiotic one and the activity of ligands could be modulated by complexation. Complex combinations of Cu(II) and Pd(II) with thiosemicarbazone derivatives of 2-hydroxy-8-R-tricyclo[7.3.1.0.(2,7)]tridecane-13-one (where R=C(3)H(7), C(4)H(3)O) were synthesized. The characterization of the ligands and the newly formed compounds was done by (1)H NMR, (13)C NMR, UV-vis, IR, ESR spectroscopy, elemental analysis, molar electric conductibility and thermal studies. Experiments performed to identify the structures proved that the ligands coordinate to metal ions in different ways - neutral bidentate or mononegative bidentate. Also, if copper(II) acetate, copper(II) nitrate, copper(II) chloride and copper(II) thiocyanate were used, the ligands coordinated in a mononegative bidentate fashion. If copper(II) sulfate was used, the ligands coordinated in a neutral bidentate fashion. The biological activity for the copper(II) synthesized compounds was assessed in terms of antibacterial or antiproliferative activity. The antibacterial activity of the complexes against Staphylococcus aureus var. Oxford 6538, Escherichia coli ATCC 10536, Klebsielle pneumoniae ATCC 100131 and Candida albicans ATCC 10231 strains was studied and compared with that of free ligands. The effect of complex compounds on the proliferation of HeLa cells was tested. For all tested complexes an antiproliferative activity was noted at concentrations higher than 1 microM, but lower than 10 microM. Therefore, complex compounds of copper(II) were synthesized, structurally characterized and tested for biological activity, proving both antibacterial and antiproliferative activity.

  13. A new approach for simultaneous determination of Co(II), Ni(II), Cu(II) and Pd(II) using 2-thiophenaldehyde-3-thiosemicarbazone as reagent by solid phase microextraction-high performance liquid chromatography.

    PubMed

    Kaur, Varinder; Aulakh, Jatinder Singh; Malik, Ashok Kumar

    2007-11-05

    A new method is proposed herein for the sorption, separation and simultaneous determination of Co(II), Ni(II), Cu(II) and Pd(II) using 2-thiophenaldehyde-3-thiosemicarbazone (TPTS) as a reagent by solid phase microextraction-high performance liquid chromatography-UV detection. The method is based upon the sorption of metal complexes on polydimethylsiloxane (PDMS) fiber from aqueous solution followed by desorption in the desorption chamber of solid phase microextraction-high performance liquid chromatography (SPME-HPLC) interface. Reversed phase high performance liquid chromatography using acetonitrile:water (65:35) as an eluent on a C18 column has been used to achieve the separation. The effects of agitation, addition of salts, extraction time and desorption time are examined to obtain optimized conditions. The detection limits for Co(II), Ni(II), Cu(II) and Pd(II) are 9, 6, 1 and 7 ng L(-1) based on 3sigma of blank response. The precision is calculated to be less than 3.5% (R.S.D.) for all species. A 10 time enhancement in the signal is observed for SPME when compared with direct analysis. The method is successfully applied to several synthetic mixtures without interference from other common metal ions such as Mo(VI), V(V), Ag(I), Sn(IV), Cd(II), Zn(II), Pb(II), Cr(III) and Cr(VI). The proposed method is tested for the determination of Co(II), Ni(II), Cu(II) and Pd(II) in alloys and water samples spiked with these metal ions.

  14. Carbonization Studies of Glassy Carbon Derived from Bis-Ortho-Diynylarenes (BODA) (Postprint)

    DTIC Science & Technology

    2007-02-26

    Derived from Bis-Ortho-Diynylarenes ( BODA ) (Postprint) 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Scott T. Iacono, Mark W. Perpall...have demonstrated bis-ortho-diynylarene ( BODA ) monomers undergo Bergman cyclopolymerizations to form hyper-branched, rigid naphthalene networks that...Std. 239.18 CARBONIZATION STUDIES OF GLASSY CARBON DERIVED FROM BIS-ORTHO-DIYNYLARENES ( BODA ) Scott T. Iacono1, Mark W. Perpall1, Wesley P

  15. 2,2-Bis[(2-halo-4-aminophenoxy)phenyl]-hexafluoropropane

    NASA Technical Reports Server (NTRS)

    Jones, Robert J. (Inventor); Chang, Glenn E. C. (Inventor)

    1985-01-01

    There are provided the aromatic diamines 2,2-bis-[(2-halo-4-aminophenoxy)-phenyl]hexafluoropropane, where the attached ortho halogen is preferably chlorine, and 4,4'-bis(4-aminophenoxy)biphenyl, as novel monomers for polyimide polymerizations. The former, when reacted with 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, provides a polyimide having exceptional high-temperature performance. The latter diamine is a low-cost monomer for polyimide production.

  16. 40 CFR 721.982 - Calcium, bis(2,4-pentanedionato-O,O′).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Calcium, bis(2,4-pentanedionato-O,Oâ²... Substances § 721.982 Calcium, bis(2,4-pentanedionato-O,O′). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance calcium, bis(2,4-pentanedionato-O,O′) (PMN P-93-214,...

  17. 40 CFR 721.982 - Calcium, bis(2,4-pentanedionato-O,O′).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Calcium, bis(2,4-pentanedionato-O,Oâ²... Substances § 721.982 Calcium, bis(2,4-pentanedionato-O,O′). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance calcium, bis(2,4-pentanedionato-O,O′) (PMN P-93-214,...

  18. Effect of bis-1,4-dihydropyridine in the kidney of diabetic rats.

    PubMed

    Gómez-Pliego, Raquel; Gómez-Zamudio, Jaime; Velasco-Bejarano, Benjamín; Ibarra-Barajas, Maximiliano; Villalobos-Molina, Rafael

    2013-01-01

    The in vivo effectiveness of 4-dihydropyridine (bis-1,4-DHP), a new calcium-channel blocker, as a nephroprotector in isolated perfused kidney was evaluated by determining its effects on parameters associated with renal injury in diabetic rats. Diabetes in male Wistar rats, control, diabetic, control + bis-1,4-DHP, and diabetic + bis-1,4-DHP, was induced by a single administration of STZ (55 mg·kg(-1), i.p.). In the drug-treated groups, treatment with bis-1,4-DHP (10 mg·kg(-1)·day(-1)) started one week before diabetes induction; bis-1,4-DHP was dissolved in DMSO (0.3%) and suspended in drinking water with carboxymethyl cellulose (3%). Parameters evaluated were body weight, blood glucose, albuminuria, proteinuria, creatinine, urea excretion, kidney's weight / body weight ratio, and kidney perfusion pressure in all rat groups at different times of diabetes (2, 4, 6, and 10 weeks). Kidney weight of diabetic rats significantly increased vs. control, control + bis-1,4-DHP, and diabetic + bis-1,4-DHP rats at different times of diabetes. The ratios % kidney weight / 100 g body weight were different between control, control + bis-1,4-DHP, and diabetic + bis-1,4-DHP rats vs. diabetic rats (P < 0.05). Kidney perfusion pressure was decreased by diabetes, while it was partially recovered by bis-1,4-DHP treatment in response to phenylephrine. Bis-1,4-DHP had a tendency to decrease hyperglycemia vs. diabetic rats, even though glycemia was too high as compared with controls, and it ameliorated albuminuria, creatinine, and urea excretion, suggesting a favorable effect on renal haemodynamics. Bis-1,4-DHP, by inhibiting Ca(2+) entrance, induced vasodilation in renal vascular bed and thus may have a nephroprotective effect against diabetes-induced renal dysfunction, but does not have significant impact on hyperglycemia.

  19. Myosin heavy chain is stabilized by BCL-2 interacting cell death suppressor (BIS) in skeletal muscle

    PubMed Central

    Hong, Jin; Park, Jun-Sub; Lee, Hyun; Jeong, Jaemin; Hyeon Yun, Hye; Yun Kim, Hye; Ko, Young-Gyu; Lee, Jeong-Hwa

    2016-01-01

    BCL-2 interacting cell death suppressor (BIS), which is ubiquitously expressed, has important roles in various cellular processes, such as apoptosis, the cellular stress response, migration and invasion and protein quality control. In particular, BIS is highly expressed in skeletal and cardiac muscles, and BIS gene mutations result in human myopathy. In this study, we show that mRNA and protein levels of BIS were markedly increased during skeletal myogenesis in C2C12 cells and mouse satellite cells. BIS knockdown did not prevent the early stage of skeletal myogenesis, but did induce muscle atrophy and a decrease in the diameter of myotubes. BIS knockdown significantly suppressed the expression level of myosin heavy chain (MyHC) without changing the expression levels of myogenic marker proteins, such as Mgn, Cav-3 and MG53. In addition, BIS endogenously interacted with MyHC, and BIS knockdown induced MyHC ubiquitination and degradation. From these data, we conclude that molecular association of MyHC and BIS is necessary for MyHC stabilization in skeletal muscle. PMID:27034027

  20. Activity-guided isolation of cytotoxic bis-bibenzyl constituents from Dumortiera hirsuta.

    PubMed

    Toyota, Masao; Ikeda, Risa; Kenmoku, Hiromichi; Asakawa, Yoshinori

    2013-01-01

    Activity-guided fractionation of the ether extract of Dumortiera hirsute (Japanese liverwort), using cytotoxicity testing with cultured HL 60 and KB cells, resulted in the isolation of a new cytotoxic bis-bibenzyl compound, along with the two known bis-bibenzyls: isomarchantin C and isoriccardin C. The structural determination of the new bis-bibenzyl through extensive NMR spectral data indicated a derivative of marchantin A, which has been isolated from the liverwort Marchantia polymorpha. The cytotoxicity of the bis-bibenzyls was evaluated by the MTT (3-(4,5-di-methylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay using cultured HL 60 and KB cells.

  1. Synthesis and characterization of bis-thiourea having amino acid derivatives

    NASA Astrophysics Data System (ADS)

    Fakhar, Imran; Yamin, Bohari M.; Hasbullah, Siti Aishah

    2016-11-01

    In this article four new symmetric bis-thiourea derivatives having amino acid linkers were reported with good yield. Isophthaloyl dichloride was used as spacer and L-alanine, L-aspartic acid, L-phenylalanine and L-glutamic acid were used as linkers. Bis-thiourea derivatives were prepared from relatively stable isophthaloyl isothiocyanate intermediate. Newly synthesized bis-thiourea derivatives were characterized by FTIR, H-NMR, 13C-NMR and CHNS-O elemental analysis techniques. Characterization data was in good agreement with the expected derivatives, hence confirmed the synthesis of four new derivatives of bis-thiourea having amino acids.

  2. Bis(1,8-anilinonaphthalenesulfonate). A novel and potent inhibitor of microtubule assembly.

    PubMed

    Horowitz, P; Prasad, V; Luduena, R F

    1984-12-10

    Two related compounds, 1,8-anilinonaphthalenesulfonate (1,8-ANS) and bis(1,8-anilinonaphthalenesulfonate) (Bis-ANS), are useful fluorescent probes for hydrophobic areas on protein molecules. Using fluorescence, we examined the binding of these compounds to bovine brain tubulin and found that Bis-ANS and 1,8-ANS bound to tubulin with Ki values of 2 and 25 microM, respectively. Bis-ANS potently inhibited the polymerization of tubulin into microtubules in vitro. In the presence of microtubule-associated protein 2, half-maximal inhibition of assembly was obtained at 3 microM Bis-ANS. In the presence of tau protein, half-maximal inhibition was obtained at 15 microM Bis-ANS. Surprisingly, 1,8-ANS, even at 200 microM, did not inhibit assembly. Scatchard analysis indicated one binding site for Bis-ANS on tubulin. Previous reports of 1,8-ANS binding to tubulin may have been influenced by the presence of Bis-ANS which until recently was a common contaminant of commercial supplies. Because of its intense fluorescence in addition to its potent inhibitory effects, Bis-ANS appears to be a useful probe to study microtubule assembly and other interactions involving tubulin.

  3. Preparation and reactivity towards hydrazines of bis(cyanamide) and bis(cyanoguanidine) complexes of the iron triad.

    PubMed

    Albertin, Gabriele; Antoniutti, Stefano; Caia, Alfonso; Castro, Jesús

    2014-05-21

    Bis(diethylcyanamide) [Fe(N≡CNEt2)2L4](BPh4)2 1a and bis(cyanoguanidine) [Fe{N≡CN(H)C(NH2)=NH}2L4](BPh4)2 1b [L = P(OEt)3] complexes were prepared by allowing iron(II) chloride to react first with an excess of P(OEt)3 and then of the appropriate cyanamide, followed by addition of an excess of NaBPh4. Instead, bis(complexes) of ruthenium and osmium [M(N≡CNEt2)2L4](BPh4)2 2a, 3a and [M{N≡CN(H)C(NH2)=NH}2L4](BPh4)2 2b, 3b (M = Ru 2, Os 3) were prepared by reacting hydrides MH2L4 first with either triflic acid HOTf or methyltriflate MeOTf and then with an excess of the appropriate cyanamide. Hydride-diethylcyanamide [MH(N≡CNEt2)L4]BPh4 4a, 5a and hydride-cyanoguanidine complexes [MH{N≡CN(H)C(NH2)=NH}L4](BPh4)2 4b, 5b (M = Ru 4, Os 5) were also obtained by reacting MH2L4 first with one equivalent of HOTf or MeOTf and then with the appropriate cyanamide. Treatment of bis(cyanamide) and bis(cyanoguanidine) complexes 1-3 with hydrazines RNHNH2 afforded hydrazinecarboximidamide derivatives [M{η(2)-N(H)=C(NEt2)N(R)NH2}L4](BPh4)2 6a-12a and [M{η(2)-N(H)=C[N=C(NH2)2]N(R)NH2}L4](BPh4)2 6b-12b (M = Fe 6-8, Ru 9, 10, Os 11, 12; R = H 6, 9, 11, Me 7, 10, 12, Ph 8). A reaction path involving nucleophilic attack by hydrazine on the cyanamide carbon atom is proposed. All the complexes were characterised by spectroscopy and X-ray crystal structure determination of [Os{η(2)-NH=C[N=C(NH2)2]N(CH3)NH2}{P(OEt)3}4](BPh4)2 12b.

  4. Does using the bispectral index (BIS) during craniotomy affect the quality of recovery?

    PubMed

    Boztuğ, Neval; Bigat, Zekiye; Akyuz, Mahmut; Demir, Suleyman; Ertok, Ertugrul

    2006-01-01

    One of the aims of neuroanesthesia is to provide early postoperative recovery and neurologic examination in patients undergoing supratentorial surgery. Our aim was to investigate the role of using the bispectral index (BIS) in recovery from anesthesia and altering drug administration in patients undergoing craniotomy. Fifty American Society of Anesthesiologists' (ASA) physical status I-II patients undergoing craniotomy were included in the study. The patients were randomly divided into two groups, and all patients received standard induction drugs, and 0.8%-1.5% sevoflurane was used for maintenance of anesthesia. In the BIS-guided group, the concentration of sevoflurane was titrated to maintain BIS at 40-60. In the control group, the anesthesiologist was blind to BIS, and the concentration of sevoflurane was changed according to the patients' hemodynamic changes. The hemodynamic data, BIS values, and sevoflurane concentrations were recorded every 15 minutes. In addition, the BIS value was recorded by the primary anesthetist in the BIS-guided group and by another independent anesthetist in the control group. At the end of the study, recovery criteria and Aldrete recovery scores were recorded every 15 minutes. Neurologic assessments were performed when the Aldrete score was 9-10. BIS values were higher, and sevoflurane concentrations (P < 0.05) and total doses of fentanyl (P < 0.01) were lower, in the BIS-guided group. Times to first spontaneous breathing, eye opening, and extubation (P = 0.035, P = 0.001, and P = 0.0001, respectively) were significantly shorter in the BIS-guided group. Time to an Aldrete score of 9-10 and adequate neurologic assessment were similar between the groups. In conclusion, BIS monitoring by supratentorial craniotomy under general anesthesia reduced the maintenance anesthetic concentration and narcotic drug usage and lowered the recovery times from general anesthesia.

  5. Triclinic Polymorph of Bis(triphenylsilyl) Oxide Toluene Disolvate

    DTIC Science & Technology

    2012-01-01

    Triclinic polymorph of bis(triphenylsilyl) oxide toluene disolvate Andrew P. Purdy,a* Emily Smoot,a‡ Ray J. Butcherb and Andrew Kerrc aNaval Research... triclinic (P1) instead of possessing the previously reported rhombohedral symmetry [Hönle et al. (1990). Acta Cryst. C46, 1982–1984]. Each of the –SiPh3... structures of related compounds, see: Glidewell & Liles (1978); Morosin & Harrah (1981); Suwińska et al. (1986). For the determination by IR

  6. Lithium solvation in bis(trifluoromethanesulfonyl)imide-based ionic liquids.

    PubMed

    Lassègues, Jean-Claude; Grondin, Joseph; Talaga, David

    2006-12-28

    The lithium solvation in (1 -x)(EMI-TFSI), xLiTFSI ionic liquids where EMI(+) is the 1-ethyl-3-methylimidazolium cation and TFSI(-) the bis(trifluoromethanesulfonyl)imide anion, is shown by Raman spectroscopy to involve essentially [Li(TFSI)(2)](-) anionic clusters for 0 < x < 0.4, but addition of stoichiometric amounts of solvents S such as oligoethers changes the lithium solvation into [Li(S)(m)](+) cationic clusters; the lithium transference number in TFSI-based ionic liquid electrolytes for lithium batteries should thus be strongly improved.

  7. Vasorelaxant effects of macrocyclic bis(bibenzyls) from liverworts.

    PubMed

    Morita, Hiroshi; Zaima, Kazumasa; Koga, Ikumi; Saito, Aiko; Tamamoto, Haruka; Okazaki, Hiroki; Kaneda, Toshio; Hashimoto, Toshihiro; Asakawa, Yoshinori

    2011-07-01

    Vasorelaxant effects of a series of bis(bibenzyls) from liverworts such as Marchantia polymorpha and Marchantia paleacea on rat aorta demonstrated that they relaxed phenylephrine (PE)-induced contractions, which may be mediated through the increased release of NO from endothelial cells as well as opening of K(+) channels, and inhibition of Ca(2+) influx through voltage-dependent Ca(2+) channels (VDCs) and/or receptor-operated Ca(2+) channels (ROCs). Structure-activity relationship based on their structures was discussed. The presence of two aromatic rings which can be connected through two atoms bridge spacer may play an important role for vasorelaxant effect.

  8. 40 CFR 721.1577 - 1,4-Benzenedicarboxylic acid, bis [4-(ethenyloxy) butyl] ester.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... ester. 721.1577 Section 721.1577 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.1577 1,4-Benzenedicarboxylic acid, bis ester. (a) Chemical substance and... acid, bis ester (PMN P-98-1163; CAS No. 117397-31-6) is subject to reporting under this section for...

  9. 40 CFR 721.10165 - Carbonotrithioic acid, bis(phenylmethyl) ester.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...(phenylmethyl) ester. 721.10165 Section 721.10165 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10165 Carbonotrithioic acid, bis(phenylmethyl) ester. (a) Chemical... carbonotrithioic acid, bis(phenylmethyl) ester (PMN P-08-138; CAS No.26504-29-0) is subject to reporting under...

  10. 40 CFR 721.10165 - Carbonotrithioic acid, bis(phenylmethyl) ester.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...(phenylmethyl) ester. 721.10165 Section 721.10165 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10165 Carbonotrithioic acid, bis(phenylmethyl) ester. (a) Chemical... carbonotrithioic acid, bis(phenylmethyl) ester (PMN P-08-138; CAS No.26504-29-0) is subject to reporting under...

  11. 40 CFR 721.1577 - 1,4-Benzenedicarboxylic acid, bis [4-(ethenyloxy) butyl] ester.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... ester. 721.1577 Section 721.1577 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.1577 1,4-Benzenedicarboxylic acid, bis ester. (a) Chemical substance and... acid, bis ester (PMN P-98-1163; CAS No. 117397-31-6) is subject to reporting under this section for...

  12. 40 CFR 721.10348 - Aspartic acid, N,N′-(iminodi-alkanediyl)bis, tetraalkane esters (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-alkanediyl)bis, tetraalkane esters (generic). 721.10348 Section 721.10348 Protection of Environment...-alkanediyl)bis, tetraalkane esters (generic). (a) Chemical substance and significant new uses subject to..., tetraalkane esters (PMNs P-06-623 and P-06-624) are subject to reporting under this section for...

  13. 40 CFR 721.1577 - 1,4-Benzenedicarboxylic acid, bis [4-(ethenyloxy) butyl] ester.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... ester. 721.1577 Section 721.1577 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.1577 1,4-Benzenedicarboxylic acid, bis ester. (a) Chemical substance and... acid, bis ester (PMN P-98-1163; CAS No. 117397-31-6) is subject to reporting under this section for...

  14. 40 CFR 721.1577 - 1,4-Benzenedicarboxylic acid, bis [4-(ethenyloxy) butyl] ester.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... ester. 721.1577 Section 721.1577 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.1577 1,4-Benzenedicarboxylic acid, bis ester. (a) Chemical substance and... acid, bis ester (PMN P-98-1163; CAS No. 117397-31-6) is subject to reporting under this section for...

  15. 40 CFR 721.10165 - Carbonotrithioic acid, bis(phenylmethyl) ester.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...(phenylmethyl) ester. 721.10165 Section 721.10165 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10165 Carbonotrithioic acid, bis(phenylmethyl) ester. (a) Chemical... carbonotrithioic acid, bis(phenylmethyl) ester (PMN P-08-138; CAS No.26504-29-0) is subject to reporting under...

  16. 40 CFR 721.10348 - Aspartic acid, N,N′-(iminodi-alkanediyl)bis, tetraalkane esters (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-alkanediyl)bis, tetraalkane esters (generic). 721.10348 Section 721.10348 Protection of Environment...-alkanediyl)bis, tetraalkane esters (generic). (a) Chemical substance and significant new uses subject to..., tetraalkane esters (PMNs P-06-623 and P-06-624) are subject to reporting under this section for...

  17. 40 CFR 721.10165 - Carbonotrithioic acid, bis(phenylmethyl) ester.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...(phenylmethyl) ester. 721.10165 Section 721.10165 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10165 Carbonotrithioic acid, bis(phenylmethyl) ester. (a) Chemical... carbonotrithioic acid, bis(phenylmethyl) ester (PMN P-08-138; CAS No.26504-29-0) is subject to reporting under...

  18. 40 CFR 721.10348 - Aspartic acid, N,N′-(iminodi-alkanediyl)bis, tetraalkane esters (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-alkanediyl)bis, tetraalkane esters (generic). 721.10348 Section 721.10348 Protection of Environment...-alkanediyl)bis, tetraalkane esters (generic). (a) Chemical substance and significant new uses subject to..., tetraalkane esters (PMNs P-06-623 and P-06-624) are subject to reporting under this section for...

  19. 40 CFR 721.1577 - 1,4-Benzenedicarboxylic acid, bis [4-(ethenyloxy) butyl] ester.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... ester. 721.1577 Section 721.1577 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.1577 1,4-Benzenedicarboxylic acid, bis ester. (a) Chemical substance and... acid, bis ester (PMN P-98-1163; CAS No. 117397-31-6) is subject to reporting under this section for...

  20. 40 CFR 721.10165 - Carbonotrithioic acid, bis(phenylmethyl) ester.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...(phenylmethyl) ester. 721.10165 Section 721.10165 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10165 Carbonotrithioic acid, bis(phenylmethyl) ester. (a) Chemical... carbonotrithioic acid, bis(phenylmethyl) ester (PMN P-08-138; CAS No.26504-29-0) is subject to reporting under...

  1. 40 CFR 721.10411 - Alkanenitrile, bis(cyanoalkyl)amino (generic) (P-07-537).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... (generic) (P-07-537). 721.10411 Section 721.10411 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10411 Alkanenitrile, bis(cyanoalkyl)amino (generic) (P-07-537). (a... generically as alkanenitrile, bis(cyanoalkyl)amino (PMN P-07-537) is subject to reporting under this...

  2. 40 CFR 721.10049 - Phenol, 4,4′- cyclohexylidene bis[2-methyl-.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Phenol, 4,4â²- cyclohexylidene bis[2... Specific Chemical Substances § 721.10049 Phenol, 4,4′- cyclohexylidene bis[2-methyl-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a...

  3. 40 CFR 721.10666 - Quaternary ammonium compounds, bis(fattyalkyl) dimethyl, salts with tannins (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...(fattyalkyl) dimethyl, salts with tannins (generic). 721.10666 Section 721.10666 Protection of Environment..., bis(fattyalkyl) dimethyl, salts with tannins (generic). (a) Chemical substance and significant new... compounds, bis(fattyalkyl) dimethyl, salts with tannins (PMN P-12-437) is subject to reporting under...

  4. Water sorption of CH3- and CF3-Bis-GMA based resins with additives

    PubMed Central

    PRAKKI, Anuradha; CILLI, Renato; VIEIRA, Ian Matos; DUDUMAS, Kristina; PEREIRA, José Carlos

    2012-01-01

    Objectives To evaluate the effect of additives on the water sorption characteristics of Bis-GMA based copolymers and composites containing TEGDMA, CH3Bis-GMA or CF3Bis-GMA. Material and methods Fifteen experimental copolymers and corresponding composites were prepared combining Bis-GMA and TEGDMA, CH3Bis-GMA or CF3Bis-GMA, with aldehyde or diketone (24 and 32 mol%) totaling 30 groups. For composites, barium aluminosilicate glass and pyrogenic silica was added to comonomer mixtures. Photopolymerization was effected by 0.2 wt% each of camphorquinone and N,N-dimethyl-p-toluidine. Specimen densities in dry and water saturated conditions were obtained by Archimedes' method. Water sorption and desorption were evaluated in a desorption-sorption-desorption cycle. Water uptake (%WU), water desorption (%WD), equilibrium solubility (ES; µg/mm3), swelling (f) and volume increase (%V) were calculated using appropriate equations. Results All resins with additives had increased %WU and ES. TEGDMA-containing systems presented higher %WU, %WD, ES, f and %V values, followed by resins based on CH3Bis-GMA and CF3Bis-GMA. Conclusions Aldehyde and diketone led to increases in the water sorption characteristics of experimental resins. PMID:23032211

  5. 40 CFR 721.10260 - Benzene, 1,3-bis(1-chloro-1-methylethyl)-.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Benzene, 1,3-bis(1-chloro-1... Specific Chemical Substances § 721.10260 Benzene, 1,3-bis(1-chloro-1-methylethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene,...

  6. 40 CFR 721.10260 - Benzene, 1,3-bis(1-chloro-1-methylethyl)-.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Benzene, 1,3-bis(1-chloro-1... Specific Chemical Substances § 721.10260 Benzene, 1,3-bis(1-chloro-1-methylethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene,...

  7. 40 CFR 721.10260 - Benzene, 1,3-bis(1-chloro-1-methylethyl)-.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Benzene, 1,3-bis(1-chloro-1... Specific Chemical Substances § 721.10260 Benzene, 1,3-bis(1-chloro-1-methylethyl)-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene,...

  8. 40 CFR 721.5860 - Methylphenol, bis(sub-sti-tuted)alkyl.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Methylphenol, bis(sub-sti-tuted)alkyl... Substances § 721.5860 Methylphenol, bis(sub-sti-tuted)alkyl. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as methylphenol,...

  9. Phosphorus-Containing Bis-allenes: Synthesis and Heterocyclization Reactions Mediated by Iodine or Copper Dibromide.

    PubMed

    Essid, I; Laborde, C; Legros, F; Sevrain, N; Touil, S; Rolland, M; Ayad, T; Volle, J-N; Pirat, J-L; Virieux, D

    2017-03-30

    Bisphosphorylallenes were easily obtained in multigram scale from the Wittig-type rearrangement of bispropargyl alcohols. Unlike other conjugated bis-allenes, these reagents underwent a double cyclization mediated by iodine or copper dibromide leading to the formation of bis-1,2-oxaphospholenes.

  10. Gray's reinforcement sensitivity model and child psychopathology: laboratory and questionnaire assessment of the BAS and BIS.

    PubMed

    Colder, Craig R; O'Connor, Roisin M

    2004-08-01

    The Behavioral Approach System (BAS) and Behavioral Inhibition System (BIS) are widely studied components of Gray's sensitivity to reinforcement model. There is growing interest in integrating the BAS and BIS into models of risk for psychopathology, however, few measures assess BAS and BIS functioning in children. We adapted a questionnaire measure and reaction time task from adult studies to assess the BAS and BIS in a sample of 9-12 year olds (N = 63; 42% female). A continuous performance task was also administered to assess physiological correlates of the BAS and BIS. Factor analysis supported 3 subdimensions of the BAS (Drive, Reward Responsivity, and Impulsivity/Fun seeking), and one dimension of the BIS (sensitivity to punishment). Results supported the utility of the questionnaire measures and reaction time task as assessments of BAS and BIS functioning. Moreover, these measures were associated with internalizing and externalizing problem behavior as expected. High levels of impulsivity/fun seeking, but not drive or reward responsivity, were associated with high levels of externalizing problems, whereas high levels of sensitivity to punishment were associated with high levels of internalizing behavior problems. The relation between physiological indices and caregiver reports of the BAS, BIS, and problem behavior were complex and not consistent with expectation.

  11. 40 CFR 721.10411 - Alkanenitrile, bis(cyanoalkyl)amino (generic) (P-07-537).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... (generic) (P-07-537). 721.10411 Section 721.10411 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10411 Alkanenitrile, bis(cyanoalkyl)amino (generic) (P-07-537). (a... generically as alkanenitrile, bis(cyanoalkyl)amino (PMN P-07-537) is subject to reporting under this...

  12. 40 CFR 721.10411 - Alkanenitrile, bis(cyanoalkyl)amino (generic) (P-07-537).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... (generic) (P-07-537). 721.10411 Section 721.10411 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10411 Alkanenitrile, bis(cyanoalkyl)amino (generic) (P-07-537). (a... generically as alkanenitrile, bis(cyanoalkyl)amino (PMN P-07-537) is subject to reporting under this...

  13. 40 CFR 721.10143 - Amines, bis (C11-14-branched and linear alkyl).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... linear alkyl). 721.10143 Section 721.10143 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10143 Amines, bis (C11-14-branched and linear alkyl). (a) Chemical..., bis (C11-14-branched and linear alkyl) (PMN P-06-733; CAS No. 900169-60-0) is subject to...

  14. 40 CFR 721.10143 - Amines, bis (C11-14-branched and linear alkyl).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... linear alkyl). 721.10143 Section 721.10143 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10143 Amines, bis (C11-14-branched and linear alkyl). (a) Chemical..., bis (C11-14-branched and linear alkyl) (PMN P-06-733; CAS No. 900169-60-0) is subject to...

  15. 40 CFR 721.10143 - Amines, bis (C11-14-branched and linear alkyl).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... linear alkyl). 721.10143 Section 721.10143 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10143 Amines, bis (C11-14-branched and linear alkyl). (a) Chemical..., bis (C11-14-branched and linear alkyl) (PMN P-06-733; CAS No. 900169-60-0) is subject to...

  16. 40 CFR 721.10143 - Amines, bis (C11-14-branched and linear alkyl).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... linear alkyl). 721.10143 Section 721.10143 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10143 Amines, bis (C11-14-branched and linear alkyl). (a) Chemical..., bis (C11-14-branched and linear alkyl) (PMN P-06-733; CAS No. 900169-60-0) is subject to...

  17. 40 CFR 721.10143 - Amines, bis (C11-14-branched and linear alkyl).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... linear alkyl). 721.10143 Section 721.10143 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10143 Amines, bis (C11-14-branched and linear alkyl). (a) Chemical..., bis (C11-14-branched and linear alkyl) (PMN P-06-733; CAS No. 900169-60-0) is subject to...

  18. The Brief Impairment Scale (Bis): A Multidimensional Scale of Functional Impairment for Children and Adolescents.

    ERIC Educational Resources Information Center

    Bird, Hector R.; Canino, Glorisa J.; Davies, Mark; Ramirez, Rafael; Chavez, Ligia; Duarte, Cristiane; Shen, Sa

    2005-01-01

    Objective: This article provides the results of the psychometric testing of the Brief Impairment Scale (BIS). The BIS is a 23-item instrument that evaluates three domains of functioning: interpersonal relations, school/work functioning, and self-care/self-fulfilment. It capitalizes on the strengths of existing global measures while addressing some…

  19. Synthesis and Properties of Bis(aniline, methyl)siloxy-octaphenylsilsesquioxane Modified Thermosetting Polyimide Oligomers

    DTIC Science & Technology

    2011-08-19

    Conference Paper 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Synthesis and Properties of Bis( aniline , methyl)siloxy...SYNTHESIS AND PROPERTIES OF BIS( ANILINE , METHYL)SILOXY-OCTAPHENYLSILSESQUIOXANE MODIFIED THERMOSETTING POLYIMIDE OLIGOMERS Gregory R. Yandek1...oxydiphenylene aniline (Kapton™) reduced its moisture uptake by 83% concurrently improving mechanical properties.4 The objective of this work is to

  20. 40 CFR 721.4520 - Isopropylidene, bis(1,1-dimethylpropyl) derivative.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) derivative. 721.4520 Section 721.4520 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.4520 Isopropylidene, bis(1,1-dimethylpropyl) derivative. (a) Chemical... isopropylidene, bis(1,1-dimethylpropyl) derivative (PMN P-85-648) is subject to reporting under this section...

  1. 40 CFR 721.4520 - Isopropylidene, bis(1,1-dimethylpropyl) derivative.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...) derivative. 721.4520 Section 721.4520 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.4520 Isopropylidene, bis(1,1-dimethylpropyl) derivative. (a) Chemical... isopropylidene, bis(1,1-dimethylpropyl) derivative (PMN P-85-648) is subject to reporting under this section...

  2. 40 CFR 721.4520 - Isopropylidene, bis(1,1-dimethylpropyl) derivative.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) derivative. 721.4520 Section 721.4520 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.4520 Isopropylidene, bis(1,1-dimethylpropyl) derivative. (a) Chemical... isopropylidene, bis(1,1-dimethylpropyl) derivative (PMN P-85-648) is subject to reporting under this section...

  3. 40 CFR 721.4520 - Isopropylidene, bis(1,1-dimethylpropyl) derivative.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) derivative. 721.4520 Section 721.4520 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.4520 Isopropylidene, bis(1,1-dimethylpropyl) derivative. (a) Chemical... isopropylidene, bis(1,1-dimethylpropyl) derivative (PMN P-85-648) is subject to reporting under this section...

  4. 40 CFR 721.4520 - Isopropylidene, bis(1,1-dimethylpropyl) derivative.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...) derivative. 721.4520 Section 721.4520 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.4520 Isopropylidene, bis(1,1-dimethylpropyl) derivative. (a) Chemical... isopropylidene, bis(1,1-dimethylpropyl) derivative (PMN P-85-648) is subject to reporting under this section...

  5. 77 FR 22668 - Amendment to the International Traffic in Arms Regulations: International Import Certificate BIS...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-04-17

    ...: International Import Certificate BIS-645P/ATF-4522/DSP-53 and Administrative Changes AGENCY: Department of State... Regulations (ITAR) to remove reference to the International Import Certificate (Form BIS-645P/ATF-4522/DSP-53). This amendment ceases the Department's practice of accepting DSP-53 submissions. Instead, the DSP-61...

  6. Kinetics of the reaction of diethylene glycol bis-chloroformate with allyl alcohol

    SciTech Connect

    Alekseev, N.N.; Shtoda, N.F.; Dzumedzei, N.V.

    1988-10-01

    The kinetics of diethylene glycol bis-chloroformate solvolysis by excess allyl alcohol in toluene and carbon tetrachloride has been studied. Under conditions of a pseudofirst order reaction with respect to diethylene glycol bis-chloroformate the activation parameters confirm an addition-detachment mechanism.

  7. 15 CFR 734.6 - Assistance available from BIS for determining licensing and other requirements.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... commodity, software, technology, or activity “subject to the EAR” is subject to licensing or other requirements under the EAR, you may ask BIS for an advisory opinion or a commodity classification determination... administering the EAR, BIS is the only agency that has the responsibility for determining whether an item...

  8. 40 CFR 721.10383 - Urea, N,N′-(methyl-1,3-phenylene)bis[N′,N′-bis[3-polyalkyleneamino]-, compd. with formaldehyde...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Urea, N,Nâ²-(methyl-1,3-phenylene)bis... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10383 Urea, N,N′-(methyl-1... urea, N,N′-(methyl-1,3-phenylene)bis -, compd. with formaldehyde polymer with phenol (PMN P-10-324)...

  9. 40 CFR 721.10383 - Urea, N,N′-(methyl-1,3-phenylene)bis[N′,N′-bis[3-polyalkyleneamino]-, compd. with formaldehyde...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Urea, N,Nâ²-(methyl-1,3-phenylene)bis... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10383 Urea, N,N′-(methyl-1... urea, N,N′-(methyl-1,3-phenylene)bis -, compd. with formaldehyde polymer with phenol (PMN P-10-324)...

  10. 40 CFR 721.10383 - Urea, N,N′-(methyl-1,3-phenylene)bis[N′,N′-bis[3-polyalkyleneamino]-, compd. with formaldehyde...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Urea, N,Nâ²-(methyl-1,3-phenylene)bis... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10383 Urea, N,N′-(methyl-1... urea, N,N′-(methyl-1,3-phenylene)bis -, compd. with formaldehyde polymer with phenol (PMN P-10-324)...

  11. The Cephalostatins 22. Synthesis of Bis-steroidal Pyrazine Pyrones

    PubMed Central

    Pettit, George R.; Moser, Bryan R.; Mendonça, Ricardo F.; Knight, John C.; Hogan, Fiona

    2012-01-01

    Cephalostatin 1 (1), a remarkably strong cancer cell growth inhibitory trisdecacyclic, bis-steroidal pyrazine isolated from the marine tube worm Cephalodiscus gilchristi, continues to be an important target for practical total syntheses and a model for the discovery of less complex structural modifications with promising antineoplastic activity. In the present study, the cephalostatin E and F rings were greatly simplified by replacement at C-17 with an α-pyrone (in 12), typical of the steroidal bufodienolides, and by a dihydro-γ-pyrone (in 16). The synthesis of pyrazine 12 from 5α-dihydrotestosterone (nine steps, 8% overall yield) provided the first route to a bis-bufadienolide pyrazine. Dihydro-γ-pyrone 16 was synthesized in eight steps from ketone 13. While only insignificant cancer cell growth inhibitory activity was found for pyrones 12 and 16, the results provided further support for the necessity of more closely approximating the natural D–F ring system of cephalostatin 1 in order to obtain potent antineoplastic activity. PMID:22607450

  12. Controlling Mechanical Properties of Bis-leucine Oxalyl Amide Gels

    NASA Astrophysics Data System (ADS)

    Chang, William; Carvajal, Daniel; Shull, Kenneth

    2011-03-01

    is-leucine oxalyl amide is a low molecular weight gelator capable of gelling polar and organic solvents. A fundamental understanding of self-assembled systems can lead to new methods in drug delivery and the design of new soft material systems. An important feature of self-assembled systems are the intermolecular forces between solvent and gelator molecule; by changing the environment the gel is in, the mechanical properties also change. In this project two variables were considered: the degree of neutralization present for the gelator molecule from neutral to completely ionized, and the concentration of the gelator molecule, from 1 weight percent to 8 weight percent in 1-butanol. Mechanical properties were studied using displacement controlled indentation techniques and temperature sweep rheometry. It has been found that properties such as the storage modulus, gelation temperature and maximum stress allowed increase with bis-leucine oxalyl amide concentration. The results from this study establish a 3-d contour map between the gelator concentration, the gelator degree of ionization and mechanical properties such as storage modulus and maximum stress allowed. The intermolecular forces between the bis-leucine low molecular weight gelator and 1-butanol govern the mechanical properties of the gel system, and understanding these interactions will be key to rationally designed self-assembled systems.

  13. Revised Reinforcement Sensitivity Theory and Laboratory Assessment of BIS and BAS in Children.

    PubMed

    Colder, Craig R; Trucco, Elisa M; Lopez, Hector I; Hawk, Larry W; Read, Jennifer P; Lengua, Liliana J; Weiczorek, William F; Eiden, Rina D

    2011-04-01

    There is considerable interest in Gray's reinforcement sensitivity theory. However, few measures of the behavioral approach (BAS) and inhibition systems (BIS) exist for children. Moreover, the theory was substantially revised a decade ago and measurement instruments are still largely based on the old theory. Our aim was to revise questionnaire and laboratory assessments of BIS and BAS for children. Performance on the Point Scoring Reaction Time Task for Children Revised (PSRTT-CR) conformed to theoretical expectations. Caregiver reports of BIS and BAS were associated with corresponding PSRTT-CR indices, suggesting cross-method convergent and discriminant validity. There was convergence with physiological correlates of BAS, but not physiological correlates of BIS. Overall, our revised measures represent promising instruments of children's BIS and BAS.

  14. Synthesis, spectroscopic properties and theoretical studies of bis-Schiff bases derived from polyamine and pyrazolones.

    PubMed

    Ren, Tiegang; Liu, Shuyun; Li, Guihui; Zhang, Jinglai; Guo, Jia; Li, Weijie; Yang, Lirong

    2012-11-01

    A series of novel bis-Schiff base were synthesized from 1-aryl-3-methyl-4-benzoyl-5-pyrazolones and diethylenetriamine (or triethylenetetramine) as the starting materials. All of these bis-Schiff bases were characterized by means of NMR, IR, and MS. The UV-vis absorption spectra and fluorescent spectra of these bis-Schiff bases were also measured. Moreover, the B3LYP/6-31G(d) method was used to optimize the ground state geometry of the bis-Schiff bases; and the UV-vis spectroscopic properties of the products were computed and compared with corresponding experimental data based on cc-pVDZ basis set of TD-B3LYP method. It has been found that all of these bis-Schiff bases show a remarkable absorption peak in a wavelength range of 270-340 nm; and their maximum emission peaks are around 348 nm.

  15. 40 CFR 721.5625 - Oxiranemethanamine, N,N′-[methylenebis(2-ethyl-4,1-phenylene)]bis[N-(oxiranylmethyl)]-.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Oxiranemethanamine, N,Nâ²- bis -. 721... Substances § 721.5625 Oxiranemethanamine, N,N′- bis -. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as oxiranemethanamine, N,N′- bis - (PMN...

  16. 40 CFR 721.5625 - Oxiranemethanamine, N,N′-[methylenebis(2-ethyl-4,1-phenylene)]bis[N-(oxiranylmethyl)]-.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Oxiranemethanamine, N,Nâ²- bis -. 721... Substances § 721.5625 Oxiranemethanamine, N,N′- bis -. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as oxiranemethanamine, N,N′- bis - (PMN...

  17. 40 CFR 721.5625 - Oxiranemethanamine, N,N′-[methylenebis(2-ethyl-4,1-phenylene)]bis[N-(oxiranylmethyl)]-.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Oxiranemethanamine, N,Nâ²- bis -. 721... Substances § 721.5625 Oxiranemethanamine, N,N′- bis -. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as oxiranemethanamine, N,N′- bis - (PMN...

  18. 40 CFR 721.5625 - Oxiranemethanamine, N,N′-[methylenebis(2-ethyl-4,1-phenylene)]bis[N-(oxiranylmethyl)]-.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Oxiranemethanamine, N,Nâ²- bis -. 721... Substances § 721.5625 Oxiranemethanamine, N,N′- bis -. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as oxiranemethanamine, N,N′- bis - (PMN...

  19. 40 CFR 721.10321 - Bis[phenyl, 2H-1,3-benzoxazine]derivative (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Bis derivative (generic). 721.10321... Substances § 721.10321 Bis derivative (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bis derivative (PMN P-03-194) is subject...

  20. 40 CFR 721.10539 - Bis[phenyl-2H-1,3-benzoxazine]derivative (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Bis derivative (generic). 721.10539... Substances § 721.10539 Bis derivative (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bis derivative (PMN P-02-653) is subject...

  1. 40 CFR 721.10321 - Bis[phenyl, 2H-1,3-benzoxazine]derivative (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Bis derivative (generic). 721.10321... Substances § 721.10321 Bis derivative (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bis derivative (PMN P-03-194) is subject...

  2. 40 CFR 721.10321 - Bis[phenyl, 2H-1,3-benzoxazine]derivative (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Bis derivative (generic). 721.10321... Substances § 721.10321 Bis derivative (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bis derivative (PMN P-03-194) is subject...

  3. 40 CFR 721.10539 - Bis[phenyl-2H-1,3-benzoxazine]derivative (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Bis derivative (generic). 721.10539... Substances § 721.10539 Bis derivative (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as bis derivative (PMN P-02-653) is subject...

  4. 40 CFR 721.5625 - Oxiranemethanamine, N,N′-[methylenebis(2-ethyl-4,1-phenylene)]bis[N-(oxiranylmethyl)]-.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Oxiranemethanamine, N,Nâ²- bis -. 721... Substances § 721.5625 Oxiranemethanamine, N,N′- bis -. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as oxiranemethanamine, N,N′- bis - (PMN...

  5. 40 CFR 721.1068 - Benzenamine, 4-isocyanato-N,N-bis(4-isocyanatophenyl)-2,5-dimethoxy-.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Benzenamine, 4-isocyanato-N,N-bis(4... New Uses for Specific Chemical Substances § 721.1068 Benzenamine, 4-isocyanato-N,N-bis(4... chemical substance identified as benzenamine, 4-isocyanato-N,N- bis(4-isocyanatophenyl)-2,5-dimethoxy-...

  6. 40 CFR 721.1068 - Benzenamine, 4-isocyanato-N,N-bis(4-isocyanatophenyl)-2,5-dimethoxy-.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Benzenamine, 4-isocyanato-N,N-bis(4... New Uses for Specific Chemical Substances § 721.1068 Benzenamine, 4-isocyanato-N,N-bis(4... chemical substance identified as benzenamine, 4-isocyanato-N,N- bis(4-isocyanatophenyl)-2,5-dimethoxy-...

  7. Ferrocene-bis(thymine/uracil) conjugates: base pairing directed, spacer dependent self-assembly and supramolecular packing.

    PubMed

    Patwa, Amit N; Gonnade, Rajesh G; Kumar, Vaijayanti A; Bhadbhade, Mohan M; Ganesh, Krishna N

    2010-12-17

    X-ray crystallographic studies of methylene linked Ferrocene-bis(thymine/uracil) conjugates Fc(T:T)(M) and Fc(U:U)(M) reveal base dependent 2-D supramolecular assemblies generated via wobble self-pairing for bis-thymine and reverse wobble self-pairing for bis-uracil conjugates, differing in architecture from the corresponding butylene spacer linked conjugates.

  8. Organoselenium bis selenide attenuates 3-nitropropionic acid-induced neurotoxicity in rats.

    PubMed

    Bortolatto, Cristiani F; Jesse, Cristiano R; Wilhelm, Ethel A; Chagas, Pietro M; Nogueira, Cristina W

    2013-04-01

    This study was designed to evaluate the effects of bis selenide on Huntington disease (HD)-like signs induced by 3-nitropropionic acid (3-NP) in rats. To this aim, rats were treated for 4 days with bis selenide (5 or 20 mg/kg/day, per oral) 30 min before 3-NP (20 mg/kg/day, intraperitoneally). The body weight gain, locomotor activity, motor coordination, and biochemical parameters in striatal preparations were assessed 24 h after the last injection of 3-NP. The highest dose of bis selenide was effective in protecting against body weight loss and motor coordination deficit induced by 3-NP. The impairment of locomotor activity caused by 3-NP was abolished by bis selenide at both doses. Bis selenide (5 and 20 mg/kg) partially restored succinate dehydrogenase activity inhibited after 3-NP exposure. The dose of 20 mg/kg of bis selenide recovered partially δ-aminolevulinic acid dehydratase activity, and totally Na(+), K(+)-ATPase activity, two sulfhydryl enzymes sensitive to oxidizing agents, which had their activities inhibited by 3-NP. Also, 3-NP led to an increase in protein carbonyl levels and glutathione reductase activity and inhibited catalase activity-alterations that were reversed by bis selenide administration at both doses. The highest dose of bis selenide was effective against the increase of RS levels, the depletion of reduced glutathione content, and the inhibition of glutathione peroxidase activity induced by 3-NP. Bis selenide was not effective against inhibition of SOD activity caused by 3-NP. These findings demonstrate that bis selenide elicited protective effects against HD-like signs induced by 3-NP in rats.

  9. Identification of a bis-molybdopterin intermediate in molybdenum cofactor biosynthesis in Escherichia coli.

    PubMed

    Reschke, Stefan; Sigfridsson, Kajsa G V; Kaufmann, Paul; Leidel, Nils; Horn, Sebastian; Gast, Klaus; Schulzke, Carola; Haumann, Michael; Leimkühler, Silke

    2013-10-11

    The molybdenum cofactor is an important cofactor, and its biosynthesis is essential for many organisms, including humans. Its basic form comprises a single molybdopterin (MPT) unit, which binds a molybdenum ion bearing three oxygen ligands via a dithiolene function, thus forming Mo-MPT. In bacteria, this form is modified to form the bis-MPT guanine dinucleotide cofactor with two MPT units coordinated at one molybdenum atom, which additionally contains GMPs bound to the terminal phosphate group of the MPTs (bis-MGD). The MobA protein catalyzes the nucleotide addition to MPT, but the mechanism of the biosynthesis of the bis-MGD cofactor has remained enigmatic. We have established an in vitro system for studying bis-MGD assembly using purified compounds. Quantification of the MPT/molybdenum and molybdenum/phosphorus ratios, time-dependent assays for MPT and MGD detection, and determination of the numbers and lengths of Mo-S and Mo-O bonds by X-ray absorption spectroscopy enabled identification of a novel bis-Mo-MPT intermediate on MobA prior to nucleotide attachment. The addition of Mg-GTP to MobA loaded with bis-Mo-MPT resulted in formation and release of the final bis-MGD product. This cofactor was fully functional and reconstituted the catalytic activity of apo-TMAO reductase (TorA). We propose a reaction sequence for bis-MGD formation, which involves 1) the formation of bis-Mo-MPT, 2) the addition of two GMP units to form bis-MGD on MobA, and 3) the release and transfer of the mature cofactor to the target protein TorA, in a reaction that is supported by the specific chaperone TorD, resulting in an active molybdoenzyme.

  10. Bis-ANS as a specific inhibitor for microtubule-associated protein induced assembly of tubulin.

    PubMed

    Mazumdar, M; Parrack, P K; Mukhopadhyay, K; Bhattacharyya, B

    1992-07-21

    5,5'-Bis[8-(phenylamino)-1-naphthalenesulfonate] (bis-ANS), the fluorescent probe which binds to tubulin, inhibits its assembly into microtubules [Horowitz et al. (1984) J. Biol. Chem. 259, 14647-14650]. The results described in this paper demonstrate that bis-ANS is quite distinct from other well-known microtubule inhibitors in its specificity of action. The inhibitory potentials of bis-ANS and its three structural analogues ANS, Prodan [6-propionyl-2-(dimethylamino)naphthalene], and NSA (naphthalenesulfonic acid) have been compared. It is found that they can be arranged in the following order according to their polymerization inhibitory potentials: bis-ANS approximately equal to Prodan much greater than ANS greater than NSA. Interestingly, the naphthalene nucleus is sufficient to cause inhibition of polymerization. Detailed experiments were carried out to examine the mode of assembly inhibition by aminonaphthalenes at the molecular level, using bis-ANS as a representative. It was found that there was little or no effect of bis-ANS on the assembly of tubulin when polymerization was induced by assembly promoters like taxol, DMSO, or glutamate, or on the assembly of subtilisin-digested protein (tubulin S), for all of which half-maximal inhibition could not be achieved even at 120 microM bis-ANS. On the contrary, bis-ANS acts as an inhibitor in the case of MAP- (MAP2 and tau) and poly(L-lysine)-induced assembly of tubulin, with half-maximal inhibitory concentrations ranging from 1.5 to 7.6 microM. Our results place bis-ANS as a novel inhibitor, which seems to specifically inhibit C-termini-mediated assembly. Of all assembly inhibitors known so far, none exhibits such selection.(ABSTRACT TRUNCATED AT 250 WORDS)

  11. A phase I and pharmacokinetic study of oral 3-aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP, NSC #663249) in the treatment of advanced stage solid cancers – A California Cancer Consortium Study

    PubMed Central

    Chao, Joseph; Synold, Timothy W.; Morgan, Robert J.; Kunos, Charles; Longmate, Jeff; Lenz, Heinz-Josef; Lim, Dean; Shibata, Stephen; Chung, Vincent; Stoller, Ronald G.; Belani, Chandra P.; Gandara, David R.; McNamara, Mark; Gitlitz, Barbara J.; Lau, Derick H.; Ramalingam, Suresh S.; Davies, Angela; Espinoza-Delgado, Igor; Newman, Edward M.; Yen, Yun

    2012-01-01

    Background 3-aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP) is a novel small molecule ribonucleotide reductase inhibitor. This study was designed to estimate the maximum-tolerated dose (MTD) and oral bioavailability of 3-AP in patients with advanced stage solid tumors. Methods Twenty patients received one dose of intravenous and subsequent cycles of oral 3-AP following a 3+3 patient dose-escalation. Intravenous 3-AP was administered to every patient at a fixed dose of 100 mg over a 2-hour infusion 1 week prior to the first oral cycle. Oral 3-AP was administered every 12 hours for 5 consecutive doses on days 1–3, days 8–10, and days 15–17 of every 28-day cycle. 3-AP was started at 50 mg with a planned dose escalation to 100, 150, and 200 mg. Dose-limiting toxicities (DLT) and bioavailability were evaluated. Results Twenty patients were enrolled. For dose level 1 (50mg), the second of three treated patients had a DLT of grade 3 hypertension. In the dose level 1 expansion cohort, three patients had no DLTs. No further DLTs were encountered during escalation until the 200 mg dose was reached. At the 200 mg 3-AP dose level, two treated patients had DLTs of grade 3 hypoxia. One additional DLT of grade 4 febrile neutropenia was subsequently observed at the de-escalated 150 mg dose. One DLT in 6 evaluable patients established the MTD as 150 mg per dose on this dosing schedule. Responses in the form of stable disease occurred in 5 (25%) of 20 patients. The oral bioavailability of 3-AP was 67 ± 29%, and was consistent with the finding that the MTD by the oral route was 33% higher than by the intravenous route. Conclusions Oral 3-AP is well-tolerated and has an MTD similar to its intravenous form after accounting for the oral bioavailability. Oral 3-AP is associated with a modest clinical benefit rate of 25% in our treated patient population with advanced solid tumors. PMID:22105720

  12. Lysosomal membrane stability plays a major role in the cytotoxic activity of the anti-proliferative agent, di-2-pyridylketone 4,4-dimethyl-3-thiosemicarbazone (Dp44mT).

    PubMed

    Gutierrez, Elaine M; Seebacher, Nicole A; Arzuman, Laila; Kovacevic, Zaklina; Lane, Darius J R; Richardson, Vera; Merlot, Angelica M; Lok, Hiu; Kalinowski, Danuta S; Sahni, Sumit; Jansson, Patric J; Richardson, Des R

    2016-07-01

    The potent and selective anti-tumor agent, di-2-pyridylketone 4,4-dimethyl-3-thiosemicarbazone (Dp44mT), localizes in lysosomes and forms cytotoxic copper complexes that generate reactive oxygen species (ROS), resulting in lysosomal membrane permeabilization (LMP) and cell death. Herein, the role of lysosomal membrane stability in the anti-tumor activity of Dp44mT was investigated. Studies were performed using molecules that protect lysosomal membranes against Dp44mT-induced LMP, namely heat shock protein 70 (HSP70) and cholesterol. Up-regulation or silencing of HSP70 expression did not affect Dp44mT-induced LMP in MCF7 cells. In contrast, cholesterol accumulation in lysosomes induced by the well characterized cholesterol transport inhibitor, 3-β-[2-(diethyl-amino)ethoxy]androst-5-en-17-one (U18666A), inhibited Dp44mT-induced LMP and markedly and significantly (p<0.001) reduced the ability of Dp44mT to inhibit cancer cell proliferation (i.e., increased the IC(50)) by 140-fold. On the other hand, cholesterol extraction using methyl-β-cyclodextrin enhanced Dp44mT-induced LMP and significantly (p<0.01) increased its anti-proliferative activity. The protective effect of U18666A in increasing lysosomal cholesterol and preventing the cytotoxic activity of Dp44mT was not due to induced autophagy. Instead, U18666A was found to decrease lysosomal turnover, resulting in autophagosome accumulation. Moreover, preincubation with U18666A did not prevent the ability of Dp44mT to induce autophagosome synthesis, indicating that autophagic initiation via Dp44mT occurs independently of LMP. These studies demonstrate the significance of lysosomal membrane stability in relation to the ability of Dp44mT to execute tumor cell death and overcome pro-survival autophagy. Hence, lysosomal-dependent cell death induced by Dp44mT serves as an important anti-tumor strategy. These results are important for comprehensively understanding the mechanism of action of Dp44mT.

  13. Preparation and crystal structure of the 1,2-dimethoxyethane complex of bis[bis(trimethylsilyl)amido]dichlorouranium(IV)

    SciTech Connect

    McCullough, Laughlin G.; Turner, Howard W.; Andersen, Richard A.; Zalkin, Allan.; Templeton, David H.

    1981-09-01

    The complex [(Me3Si)2N]2UCl2(1,2-dimethoxyethane) has been prepared for this study from uranium tetrachloride and two molar equivalents of sodium bis(trimethylsilyl)amide in 1,2-dimethoxyethane. It may also be prepared from uranium tetrachloride and two molar equivalents of sodium bis(trimethylsilyl)amide in tetrahydrofuran followed by addition of 1,2-dimethyoxyethane. The green pentane-soluble complex crystallizes in space group Pbca with cell dimensions a = 15.207(4) Å, b= 12.021(3) Å, and c = 33.429(9) Å, Z = 8, and dx = 1.57 g cm-3. The uranium atom, which has approximate C2 symmetry, is coordinated to two nitrogen atoms from the amide groups, two oxygen atoms from the dimethoxyethane group, and two chlorine atoms. Lastly, the average U-N, U-O, and U-Cl distances are 2.23, 2.59, and 2.64 Å, respectively.

  14. Di-mu-hydroxido-bis{[bis(6-methyl-2-pyridylmethyl)(2-phenylethyl)amine-kappa(3)N',N'',N''']copper(II)} bis(perchlorate).

    PubMed

    García, Ana María; Manzur, Jorge; Vega, Andrés

    2007-07-01

    The title compund, [Cu(2)(OH)(2)(C(22)H(25)N(3))(2)](ClO(4))(2), is a copper(II) dimer, with two [CuL](2+) units [L is bis(6-methyl-2-pyridylmethyl)(2-phenylethyl)amine] bridged by hydroxide groups to define the {[CuL](mu-OH)(2)[CuL]}(2+) cation. Charge balance is provided by perchlorate counter-anions. The cation has a crystallographic inversion centre halfway between the Cu(II) ions, which are separated by 3.0161 (8) Angstrom. The central core of the cation is an almost regular Cu(2)O(2) parallelogram of sides 1.931 (2) and 1.935 (2) Angstrom, with a Cu-O-Cu angle of 102.55 (11) degrees . The coordination geometry around each Cu(II) centre can be best described as a square-based pyramid, with three N atoms from L ligands and two hydroxide O atoms completing the coordination environment. Each cationic unit is hydrogen bonded to two perchlorate anions by means of hydroxide-perchlorate O-H...O interactions.

  15. Validity and Reliability of the Abbreviated Barratt Impulsiveness Scale in Spanish (BIS-15S)*

    PubMed Central

    Orozco-Cabal, Luis; Rodríguez, Maritza; Herin, David V.; Gempeler, Juanita; Uribe, Miguel

    2010-01-01

    Objective This study determined the validity and reliability of a new, abbreviated version of the Spanish Barratt Impulsiveness Scale (BIS-15S) in Colombian subjects. Method The BIS-15S was tested in non-clinical (n=283) and clinical (n=164) native Spanish-speakers. Intra-scale reliability was calculated using Cronbach’s α, and test-retest reliability was measured with Pearson correlations. Psychometric properties were determined using standard statistics. A factor analysis was performed to determine BIS-15S factor structure. Results 447 subjects participated in the study. Clinical subjects were older and more educated compared to non-clinical subjects. Impulsivity scores were normally distributed in each group. BIS-15S total, motor, non-planning and attention scores were significantly lower in non-clinical vs. clinical subjects. Subjects with substance-related disorders had the highest BIS-15S total scores, followed by subjects with bipolar disorders and bulimia nervosa/binge eating. Internal consistency was 0.793 and test-retest reliability was 0.80. Factor analysis confirmed a three-factor structure (attention, motor, non-planning) accounting for 47.87% of the total variance in BIS-15S total scores. Conclusions The BIS-15S is a valid and reliable self-report measure of impulsivity in this population. Further research is needed to determine additional components of impulsivity not investigated by this measure. PMID:21152412

  16. Synthesis of lyso(bis)phosphatidic acid in rabbit alveolar macrophages

    SciTech Connect

    Thornburg, T.; Roddick, V.; Wykle, R.L.; Waite, M.

    1987-05-01

    Reported here are studies on the biosynthetic pathway used by normal and BCG elicited alveolar macrophages for the synthesis of lyso(bis)phosphatidic acid (L(bis)PA). Earlier observations by this laboratory have shown that although L(bis)PA is abundant in these cells, there is little de novo synthesis of this lipid. Diaceyl phosphatidylglycerol (PG) labeled with either (1,2,3-/sup 3/H) glycerol or /sup 32/P demonstrated that PG is used as an exogenous substrate for L(bis)PA formation; both glycerol moieties are incorporated. Other phospholipids do not have this capacity. BCG-elicited macrophages are capable of only one-quarter the synthesis of L(bis)PA seen with normal cells, and also show a decreased amount of cell associated substrate. In addition, (/sup 3/H) 1-0-alkyl PG was used as a substrate to test the importance of the sn-1 acyl linkage in the synthetic pathway. This substrate produced less L(bis)PA while dramatically increasing the amounts of labelled phosphatidylethanolamine and phosphatidylcholine within the cell. The alkyl substrate also showed increased uptake by the cell. They conclude that the hydrolysis of the acyl group at the sn-1 position of PG is essential in the synthetic pathway leading to the production of L(bis)PA. They further suggest that the PG used by these cells as an exogenous substrate in vitro is obtained from the PG-rich surfactant surrounding the alveolar macrophage.

  17. Crystalline Bis-urea Nanochannel Architectures Tailored for Single-File Diffusion Studies.

    PubMed

    Bowers, Clifford R; Dvoyashkin, Muslim; Salpage, Sahan R; Akel, Christopher; Bhase, Hrishi; Geer, Michael F; Shimizu, Linda S

    2015-06-23

    Urea is a versatile building block that can be modified to self-assemble into a multitude of structures. One-dimensional nanochannels with zigzag architecture and cross-sectional dimensions of only ∼3.7 Å × 4.8 Å are formed by the columnar assembly of phenyl ether bis-urea macrocycles. Nanochannels formed by phenylethynylene bis-urea macrocycles have a round cross-section with a diameter of ∼9.0 Å. This work compares the Xe atom packing and diffusion inside the crystalline channels of these two bis-ureas using hyperpolarized Xe-129 NMR. The elliptical channel structure of the phenyl ether bis-urea macrocycle produces a Xe-129 powder pattern line shape characteristic of an asymmetric chemical shift tensor with shifts extending to well over 300 ppm with respect to the bulk gas, reflecting extreme confinement of the Xe atom. The wider channels formed by phenylethynylene bis-urea, in contrast, present an isotropic dynamically average electronic environment. Completely different diffusion dynamics are revealed in the two bis-ureas using hyperpolarized spin-tracer exchange NMR. Thus, a simple replacement of phenyl ether with phenylethynylene as the rigid linker unit results in a transition from single-file to Fickian diffusion dynamics. Self-assembled bis-urea macrocycles are found to be highly suitable materials for fundamental molecular transport studies on micrometer length scales.

  18. Protective action of methylglyoxal bis (guanylhydrazone) on the mitochondrial membrane.

    PubMed

    Toninello, A; Siliprandi, D; Castagnini, P; Novello, M C; Siliprandi, N

    1988-09-15

    At low concentrations (0.5-1.0 mM) methylglyoxal bis (guanylhydrazone) (MGBG) exhibited a clearcut protection of rat liver mitochondria against the deenergizing action of either Ca2+, or oxidizing agents (butylhydroperoxide and oxaloacetate). Such a protection resulted from the prevention of transmembrane potential decay, discharge of accumulated Ca2+, release of mitochondrial Mg2+, adenine nucleotides and pyridine nucleotides and mitochondrial swelling. At high concentrations (5-10 mM) MGBG induced functional alterations of mitochondria (decrease of transmembrane potential, lower capability to accumulate and to retain Ca2+) which can be reversed by resuspension of mitochondria in a MGBG free medium. These reversible mitochondrial alterations by high MGBG concentrations are interpreted as a consequence of an aggregation and coprecipitation of suspended mitochondria.

  19. Macrocyclic bis(ureas) as ligands for anion complexation

    PubMed Central

    Kretschmer, Claudia; Dittmann, Gertrud

    2014-01-01

    Summary Two macrocyclic bis(ureas) 1 and 2, both based on diphenylurea, have been synthesized. Compound 1 represents the smaller ring with two ethynylene groups as linkers and 2 the larger ring with two butadiynylene groups. On thermal treatment to 130 °C molecule 1 splits up into two dihydroindoloquinolinone (3) molecules. Both compounds 1 and 2 form adducts with polar molecules such as dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) and act as complexing agents towards a series of anions (Cl−, Br−, I−, NO3 −, HSO4 −). The crystal structures of 3, 2·2DMSO, 2·2DMF, and of the complex NEt4[Br·2] have been determined. Quantitative investigations of the complexation equilibria were performed via 1H NMR titrations. While 1 is a rather weak complexing agent, the large ring of 2 binds anions with association constants up to log K = 7.93 for chloride ions. PMID:25161744

  20. Crystal structure of BIS(Betaine) hydrochloride monohydrate

    NASA Astrophysics Data System (ADS)

    Chen, Xiao-Ming; Mak, Thomas C. W.

    1990-11-01

    Bis(betaine) hydrochloride monohydrate, 2Me 3NCH 2COO·HCI·H 2O, crystallizes in space group Pnma (No. 62), with a=11.904(1), b=22.454(5), c=5.624(1) Å, and Z=4. The structure has been refined to RinF=0.046 for 863 observed (| Fo||>6σ| Fo|) Mo Kα data. the carboxylate groups of a pair of betaine molecules are bridged by a proton to form a centrosymmetric dimer featuring a very strong hydrogen bond of length 2.454(4) Å. The crystal structure comprises a packing of such [(Me 3NCH 2COO) 2H] + moieties and hydrogen-bonded (Cl -·H 2O) ∞ zigzag chains running parallel to the c axis.

  1. Crystal structure of bis(pyridine betaine) hydrochloride monohydrate

    NASA Astrophysics Data System (ADS)

    Xiao-Ming, Chen; Mak, Thomas C. W.

    1990-04-01

    Bis(pyridine betaine) hydrochloride monohydrate, 2C 5H 5NCH 2COO·HCl·H 2O, crystallizes in space group Pnna (No. 52), with a=15.623(3), b=19.707(3), c=5.069(1) Å, and Z=4. The structure has been refined to RF=0.067 for 1207 observed (| F0|>6σ| F0|) Mo Kα data. The carboxylate groups of a pair of pyridine betaine molecules are bridged by a proton to form a centrosymmetric dimer featuring a very strong hydrogen bond of length 2.436(6) Å. The crystal structure comprises a packing of such [(C 5H 5NCH 2COO) 2H] + moieties and hydrogen-bonded (Cl -{dH 2O} ∞) zigzag chains running parallel to the c axis.

  2. In vitro microbiological evaluation of novel bis pyrazolones.

    PubMed

    Narayana Rao, D V; Raghavendra Guru Prasad, A; Spoorthy, Y N; Raghunatha Rao, D; Ravindranath, L K

    2014-03-01

    Two series of bis pyrazolones (one with 3-methyl substituent and the other one with 3-amino substituent on the pyrazolone ring) were synthesized by the cyclization reaction between various hydrazides with esters/cyano esters in ethanolic medium. Structures of newly synthesized compounds were confirmed by elemental analysis, IR, (1)H NMR and mass spectral data. These compounds were screened for antibacterial and antifungal activities. The compounds of series 3 with amino substituent demonstrated better activity than the compounds of series 2 with methyl substituent on the pyrazolone ring. Compounds "e, f, c and d" showed higher antimicrobial activity than the compounds "b and a". The antimicrobial potentials of the synthesized compounds were compared with that of standards.

  3. Tetrapyrazineplatinum(II) bis(tetrafluoroborate) acetonitrile hemisolvate

    SciTech Connect

    Derry, Paul J.; Wang, Xiaoping; Smucker, Bradley W.

    2008-01-01

    The improved synthesis and characterization of tetrapyrazineplatinum(II) bis(tetrafluoroborate) acetonitrile hemisolvate, [Pt(C4H4N2)4](BF4)2 0.5CH3CN, is reported. The unit cell contains a half equivalent of an acetonitrile solvent molecule per tetrapyrazineplatinum(II) ion. The coordination geometry of the PtII ion is almost square-planar, with the Pt atom residing on an inversion center. The BF4- counter-anion, located at a general position, has an idealized tetrahedral geometry and an acetonitrile solvent molecule, the methyl group of which is disordered over two equal positions, sits on a twofold rotation axis.

  4. Ultrathin polycrystalline 6,13-Bis(triisopropylsilylethynyl)-pentacene films

    SciTech Connect

    Jung, Min-Cherl; Zhang, Dongrong; Nikiforov, Gueorgui O.; Lee, Michael V.; Qi, Yabing; Joo Shin, Tae; Ahn, Docheon; Lee, Han-Koo; Baik, Jaeyoon; Shin, Hyun-Joon

    2015-03-15

    Ultrathin (<6 nm) polycrystalline films of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-P) are deposited with a two-step spin-coating process. The influence of spin-coating conditions on morphology of the resulting film was examined by atomic force microscopy. Film thickness and RMS surface roughness were in the range of 4.0–6.1 and 0.6–1.1 nm, respectively, except for small holes. Polycrystalline structure was confirmed by grazing incidence x-ray diffraction measurements. Near-edge x-ray absorption fine structure measurements suggested that the plane through aromatic rings of TIPS-P molecules was perpendicular to the substrate surface.

  5. 4-[Bis(4-fluorophenyl)methyl]piperazin-1-ium picrate

    PubMed Central

    Betz, Richard; Gerber, Thomas; Hosten, Eric; Dayananda, Alaloor S.; Yathirajan, Hemmige S.; Narayana, Badiadka

    2011-01-01

    The title compound {systematic name: 4-[bis(4-fluorophenyl)methyl]piperazin-1-ium 2,4,6-tri­nitro­phenolate}, C17H19F2N2 +·C6H2N3O7 −, is the picrate salt of a piperazine-supported amine bearing a benzhydryl substituent on one of its N atoms. During co-crystallisation, protonation took place on the N atom of the secondary amine functionality. The non-aromatic six-membered heterocycle adopts a chair conformation. In the crystal, N—H⋯O hydrogen bonds as well as C—H⋯O contacts connect the components into a three-dimensional network. PMID:22064439

  6. Conductivity of oriented bis-azo polymer films.

    PubMed

    Apitz, Dirk; Bertram, Ralph Peter; Benter, Nils; Sommer-Larsen, Peter; Johansen, Per Michael; Buse, Karsten

    2006-02-13

    The conductivity properties of electro-optic, photoaddressable, dense bis-azo chromophore polymer films are investigated by using samples corona poled at various temperatures. A dielectric spectrometer is applied to measure the frequency dependence of the conductivity at different temperatures before and after heating the material to above the glass transition temperature. The results show that the orientation of the chromophores changes the charge-carrier mobility. Ionic conductivity dominates in a more disordered configuration of the material, while the competing process of hole hopping takes over as a transition to a liquid-crystalline phase occurs when the material is heated to much higher than the glass transition temperature. Such microcrystallization strongly enhances the conductivity.

  7. Synthesis and spectral properties of some bis-substituted formazans

    NASA Astrophysics Data System (ADS)

    Tezcan, Habibe

    2008-03-01

    Novel, 1,4-bis-[3,3'-phenyl-5,5'-( o-carboxyphenyl)-formaz-1-yl]-benzene- o-sulphonic acid and its derivatives contained sbnd OH group at the o-, m-, p-positions of the 3-phenyl ring were synthesized. The structures of the formazans were confirmed by elemental analyses, GC-mass, IR, 1H NMR, UV-vis spectra. Their absorption properties were investigated. It was seen that λmax values shifted towards shorter wave lengths by 130 nm in CSPF relative to 1,3,5-triphenylformazan (TPF) due to the fact that the structure of CSPF contained electron withdrawing sbnd COOH and sbnd SO 3H groups (hypsochromic effect). With binding of sbnd OH group to 3-phenyl ring of CSPF, it was observed a small bathochromic effect in accordance to the electron donating effect of sbnd OH group.

  8. Manipulating RuBisCO accumulation in the green alga, Chlamydomonas reinhardtii.

    PubMed

    Johnson, Xenie

    2011-07-01

    The nuclear factor, Maturation/stability of RbcL (MRL1), regulates the accumulation of the chloroplast rbcL gene transcript in Chlamydomonas reinhardtii by stabilising the mRNA via its 5' UTR. An absence of MRL1 in algal mrl1 mutants leads to a complete absence of RuBisCO large subunit protein and thus a lack of accumulation of the RuBisCO holoenzyme. By complementing mrl1 mutants by random transformation of the nuclear genome with the MRL1 cDNA, different levels of rbcL transcript accumulate. We also observe that RuBisCO Large Subunit accumulation is perturbed. Complemented strains accumulating as little as 15% RuBisCO protein can grow phototrophically while RuBisCO in this range is limiting for phototrophic growth. We also observe that photosynthetic activity, here measured by the quantum yield of PSII, appears to be a determinant for phototrophic growth. In some strains that accumulate less RuBisCO, a strong production of reactive oxygen species is detected. In the absence of RuBisCO, oxygen possibly acts as the PSI terminal electron acceptor. These results show that random transformation of MRL1 into mrl1 mutants can change RuBisCO accumulation allowing a range of phototrophic growth phenotypes. Furthermore, this technique allows for the isolation of strains with low RuBisCO, within the range of acceptable photosynthetic growth and reasonably low ROS production. MRL1 is thus a potential tool for applications to divert electrons away from photosynthetic carbon metabolism towards alternative pathways.

  9. Neuroprotective copper bis(thiosemicarbazonato) complexes promote neurite elongation.

    PubMed

    Bica, Laura; Liddell, Jeffrey R; Donnelly, Paul S; Duncan, Clare; Caragounis, Aphrodite; Volitakis, Irene; Paterson, Brett M; Cappai, Roberto; Grubman, Alexandra; Camakaris, James; Crouch, Peter J; White, Anthony R

    2014-01-01

    Abnormal biometal homeostasis is a central feature of many neurodegenerative disorders including Alzheimer's disease (AD), Parkinson's disease (PD), and motor neuron disease. Recent studies have shown that metal complexing compounds behaving as ionophores such as clioquinol and PBT2 have robust therapeutic activity in animal models of neurodegenerative disease; however, the mechanism of neuroprotective action remains unclear. These neuroprotective or neurogenerative processes may be related to the delivery or redistribution of biometals, such as copper and zinc, by metal ionophores. To investigate this further, we examined the effect of the bis(thiosemicarbazonato)-copper complex, Cu(II)(gtsm) on neuritogenesis and neurite elongation (neurogenerative outcomes) in PC12 neuronal-related cultures. We found that Cu(II)(gtsm) induced robust neurite elongation in PC12 cells when delivered at concentrations of 25 or 50 nM overnight. Analogous effects were observed with an alternative copper bis(thiosemicarbazonato) complex, Cu(II)(atsm), but at a higher concentration. Induction of neurite elongation by Cu(II)(gtsm) was restricted to neurites within the length range of 75-99 µm with a 2.3-fold increase in numbers of neurites in this length range with 50 nM Cu(II)(gtsm) treatment. The mechanism of neurogenerative action was investigated and revealed that Cu(II)(gtsm) inhibited cellular phosphatase activity. Treatment of cultures with 5 nM FK506 (calcineurin phosphatase inhibitor) resulted in analogous elongation of neurites compared to 50 nM Cu(II)(gtsm), suggesting a potential link between Cu(II)(gtsm)-mediated phosphatase inhibition and neurogenerative outcomes.

  10. Neuroprotective Copper Bis(thiosemicarbazonato) Complexes Promote Neurite Elongation

    PubMed Central

    Bica, Laura; Liddell, Jeffrey R.; Donnelly, Paul S.; Duncan, Clare; Caragounis, Aphrodite; Volitakis, Irene; Paterson, Brett M.; Cappai, Roberto; Grubman, Alexandra; Camakaris, James; Crouch, Peter J.; White, Anthony R.

    2014-01-01

    Abnormal biometal homeostasis is a central feature of many neurodegenerative disorders including Alzheimer's disease (AD), Parkinson's disease (PD), and motor neuron disease. Recent studies have shown that metal complexing compounds behaving as ionophores such as clioquinol and PBT2 have robust therapeutic activity in animal models of neurodegenerative disease; however, the mechanism of neuroprotective action remains unclear. These neuroprotective or neurogenerative processes may be related to the delivery or redistribution of biometals, such as copper and zinc, by metal ionophores. To investigate this further, we examined the effect of the bis(thiosemicarbazonato)-copper complex, CuII(gtsm) on neuritogenesis and neurite elongation (neurogenerative outcomes) in PC12 neuronal-related cultures. We found that CuII(gtsm) induced robust neurite elongation in PC12 cells when delivered at concentrations of 25 or 50 nM overnight. Analogous effects were observed with an alternative copper bis(thiosemicarbazonato) complex, CuII(atsm), but at a higher concentration. Induction of neurite elongation by CuII(gtsm) was restricted to neurites within the length range of 75–99 µm with a 2.3-fold increase in numbers of neurites in this length range with 50 nM CuII(gtsm) treatment. The mechanism of neurogenerative action was investigated and revealed that CuII(gtsm) inhibited cellular phosphatase activity. Treatment of cultures with 5 nM FK506 (calcineurin phosphatase inhibitor) resulted in analogous elongation of neurites compared to 50 nM CuII(gtsm), suggesting a potential link between CuII(gtsm)-mediated phosphatase inhibition and neurogenerative outcomes. PMID:24587210

  11. Correlation between Pi-Orbital Overlap and Conductivity Bis- Phthalocyaninato Lanthanides

    DTIC Science & Technology

    1991-06-10

    Overlap and Conductivity Bis-Phthalo- cyaninato Lanthanides 12. PERSONAL AUTHOR(S) Juan Padilla and William E. Hatfield 13a. TYPE OF REPORT 13b TIME COVERED...phthalocyanine ligands. Conductivity measurements on the iodine-doped bis-phthalocyaninato lanthanides , H[M(Pc)l2 1, show an average increase of four...18. Continued: bis-phthalocyaninato lanthanides mobility model OFFICE OF NAVAL RESERACH Just if o1 Contract N0014-89-J-1734 * R&T Code .135007---05 0

  12. Effect of three bis-pyridyl-bis-amide ligands with various spacers on the structural diversity of new multifunctional cobalt(II) coordination polymers

    SciTech Connect

    Lin, Hong-Yan; Lu, Huizhe; Le, Mao; Luan, Jian; Wang, Xiu-Li; Liu, Guocheng; Zhang, Juwen

    2015-03-15

    Three new cobalt(II) coordination polymers [Co{sub 2}(1,4-NDC){sub 2}(3-bpye)(H{sub 2}O)] (1), [Co(1,4-NDC)(3-bpfp)(H{sub 2}O)] (2) and [Co(1,4-NDC)(3-bpcb)] (3) [3-bpye=N,N′-bis(3-pyridinecarboxamide)-1,2-ethane, 3-bpfp=bis(3-pyridylformyl)piperazine, 3-bpcb=N,N′-bis(3-pyridinecarboxamide)-1,4-benzene, and 1,4-H{sub 2}NDC=1,4-naphthalenedicarboxylic acid] have been hydrothermally synthesized. The structures of complexes 1–3 have been determined by X-ray single crystal diffraction analyses and further characterized by infrared spectroscopy (IR), powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8}) topology constructed from 3D [Co{sub 2}(1,4-NDC){sub 2}(H{sub 2}O)]{sub n} framework and bidentate 3-bpye ligands. Complex 2 shows 1D “cage+cage”-like chain formed by 1D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} ribbon chains and [Co{sub 2}(3-bpfp){sub 2}] loops, which are further linked by hydrogen bonding interactions to form a 3D supramolecular network. Complex 3 displays a 3D coordination network with a 6-connected (4{sup 12}.6{sup 3}) topology based on 2D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} layers and bidentate 3-bpcb bridging ligands. The influences of different bis-pyridyl-bis-amide ligands with various spacers on the structures of title complexes are studied. Moreover, the fluorescent properties, electrochemical behaviors and magnetic properties of complexes 1–3 have been investigated. - Graphical abstract: Three multifunctional cobalt(II) complexes constructed from three bis-pyridyl-bis-amide and 1,4-naphthalenedicarboxylic acid have been hydrothermally synthesized and characterized. The fluorescent, electrochemical and magnetic properties of 1–3 have been investigated. - Highlights: • Three multifunctional cobalt(II) complexes based on various bis-pyridyl-bis-amide ligands. • Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8

  13. Coordination chemistry of 1,4-bis[bis(2-pyridylmethyl)aminomethyl]benzene with copper(II)

    NASA Astrophysics Data System (ADS)

    Louka, Febee R.; Spell, Mark L.; Grebowicz, Janusz; Albering, Jörg H.; Mautner, Franz A.; Massoud, Salah S.

    2011-05-01

    The interaction of 1,4-bis[bis(2-pyridylmethyl)aminomethyl]benzene ( p-Xy DPA) with CuCl 2·2H 2O has resulted in the isolation of the dinuclear compound [Cu 2( p-Xy DPA)Cl 4]·H 2O ( 1). When the reaction was performed in presence of sodium perchlorate, sodium azide, sodium dicyanamide (Nadca) and disodium squarate (Na 2C 4O 4) the compounds [Cu 2( p-Xy DPA)(ClO 4) 2Cl 2] ( 2), [Cu 2( p-Xy DPA)(N 3) 4]·2H 2O ( 3), [Cu 2( p-Xy DPA)(dca) 4]·4H 2O ( 4), and [Cu 2( p-Xy DPA)Cl 2(H 2O) 2](C 4O 4)·5.4H 2O ( 5) were obtained, respectively. The complexes were characterized by IR and UV-vis. spectroscopy. The visible spectra of the complexes revealed the square pyramidal geometry around the central Cu 2+ ions. The molecular structures of the complexes 2, 3, 4 and 5 were determined by single crystal X-ray crystallography. This study revealed the dinuclear nature of the complexes and showed that the Cu(II) centers have distorted five-coordinate square pyramidal geometry with N 3-donor atoms of the dipicolyl amine arms and the remaining coordination positions are occupied by the chloro and perchlorato ligands in 2, the monodentate azido ligands in 3 or the monodentate terminal nitrile dca in 4 and by the chloro and aqua ligands in 5 with the squarate dianion as counter ion.

  14. Interactive Effects of the BIS and the BAS on Trajectories of Alcohol Misuse after University Graduation

    PubMed Central

    Keough, Matthew T.; O’Connor, Roisin M.

    2015-01-01

    Reinforcement Sensitivity Theory predicts that those with a strong behavioral inhibition system (BIS) likely experience considerable anxiety and uncertainty during the transition out of university. Accordingly, they may continue to drink heavily to cope during this time (a period associated with normative reductions in heavy drinking), but only if they also have a strong behavioral approach system (BAS) to enhance the anxiolytic effects of drinking. The purpose of this study was to test this hypothesis. Participants completed online measures prior to and at 3-month intervals over the course of the year following graduation. As hypothesized, results showed that an elevated BIS predicted impeded maturing out, but only when the impulsivity facet of BAS was also elevated. In contrast, a strong BIS predicted rapid maturing out if BAS impulsivity was weak. Study findings advance our understanding of BIS-related alcohol misuse trajectories in young adulthood and provide direction for clinical interventions. PMID:26823652

  15. Tandem bis-aza-Michael addition reaction of amines in aqueous medium promoted by polystyrenesulfonic Acid

    EPA Science Inventory

    An efficient and environmentally benign tandem bis-aza-Michael addition of amines catalyzed by polystyrene sulfonic acid (PSSA) is described. This operationally simple high yielding microwave assisted synthetic protocol proceeded in water in the absence of any organic solvent.

  16. Heteroleptic bis(dipyrrinato)copper(II) and nickel(II) complexes.

    PubMed

    Toyoda, Ryojun; Tsuchiya, Mizuho; Sakamoto, Ryota; Matsuoka, Ryota; Wu, Kuo-Hui; Hattori, Yohei; Nishihara, Hiroshi

    2015-09-14

    Heteroleptic bis(dipyrrinato)copper(II) and nickel(II) complexes are synthesized. Their structures are determined by X-ray diffraction analysis, and their properties are investigated by using cyclic voltammetry, chronocoulometry, and UV/vis absorption spectroscopy.

  17. A macrocyclic bis-acridine shifts the equilibrium from duplexes towards DNA hairpins.

    PubMed Central

    Slama-Schwok, A; Peronnet, F; Hantz-Brachet, E; Taillandier, E; Teulade-Fichou, M P; Vigneron, J P; Best-Belpomme, M; Lehn, J M

    1997-01-01

    Nucleic acids can undergo dynamic conformational changes associated with the regulation of biological processes. A molecule presenting larger affinities for alternative structures relative to a duplex is expected to modify such conformational equilibria. We have previously reported that macrocyclic bis-acridine binds preferentially to single-stranded regions, especially DNA hairpins, due to steric effects. Here, we show, using gel electrophoresis, fluorescence and melting temperature experiments, that the macrocycle bis-acridine shifts an equilibrium from a duplex towards the corresponding hairpins. Competition experiments enlighten the higher affinity of the macrocycle for hairpins compared with double-stranded DNA. The macrocycle bis-acridine destabilizes a synthetic polynucleotide, by the formation of premelted areas. By extrapolation, the macrocycle bis-acridine should be able to disrupt, at least locally, genomic DNA duplexes and to stabilize unpaired areas, especially palindromic ones forming hairpins. Such macrocyclic compounds may have potential applications in the therapy of diseases involving hairpins. PMID:9185566

  18. Intramolecular aggregation and optical limiting properties of triazine-linked mono-, bis- and tris-phthalocyanines.

    PubMed

    Chen, Jun; Zhang, Tao; Wang, Shuangqing; Hu, Rui; Li, Shayu; Ma, Jin Shi; Yang, Guoqiang

    2015-10-05

    A series of triazine-linked mono-, bis- and tris-phthalocyanines are synthesized, intramolecular aggregation is found in bis- and tris-phthalocyanines via π-π stacking interaction. Theoretical and experimental studies reveal the formation of the intramolecular aggregation. The spectrographic, photophysical and nonlinear optical properties of these compounds are adjusted for the formation of the intramolecular aggregation. The bis-phthalocyanine dimer presents smaller fluorescence quantum yield, lower triplet formation yield and the triplet-minus-ground state extinction coefficient, which causes poorer optical limiting performance. It is interesting that the tris-phthalocyanine is composed of a mono-phthalocyanine part and a bis-phthalocyanine part, the optical limiting property of the tris-phthalocyanine is similar to that of mono-phthalocyanine.

  19. Ruthenium complexes containing bis-benzimidazole derivatives as a new class of apoptosis inducers.

    PubMed

    Li, Linlin; Wong, Yum-Shing; Chen, Tianfeng; Fan, Cundong; Zheng, Wenjie

    2012-01-28

    A series of ruthenium complexes containing bis-benzimidazole derivatives have been synthesized and identified as able to target mitochondria and induce caspase-dependent apoptosis in cancer cells through superoxide overproduction.

  20. Toxicity of some bis Mannich bases and corresponding piperidinols in the brine shrimp (Artemia salina) bioassay.

    PubMed

    Gul, H Inci; Gul, Mustafa; Erciyas, Ercin

    2003-01-01

    Some acetophenone-derived bis Mannich bases were synthesized: bis[beta-benzoylethyl]ethylamine hydrochloride (IIa), bis[beta-(p-methylbenzoyl)ethyl]ethylamine hydrochloride (IIb), bis[beta-(p-chlorobenzoyl)ethyl]ethy- lamine hydrochloride (IId), bis[(2-thienylcarbonyl)ethyl]ethylamine hydrochloride (IIe); some corresponding piperidinol derivatives: 3-benzoyl-1-ethyl-4-phenyl-4-piperidinol hydrochloride (IIIa), 1-ethyl-3-(p-methyl- benzoyl)-4-(p-methylphenyl)-4-piperidinol hydrochloride (IIIb), 1-ethyl-3-(p-methoxybenzoyl)-4-(p-methoxy- phenyl)-4-piperidinol hydrochloride (IIIc), 1-ethyl-3-(p-chlorobenzoyl)-4-(p-chlorophenyl)-4-piperidinol hydrochloride (IIId), 1-ethyl-4-(2-thienyl)-3-(2-thienylcarbonyl)-4-piperidinol hydrochloride (IIIe); and some representative quaternary piperidinols: 3-benzoyl-1-ethyl-4-hydroxy-1-methyl-4-phenylpiperidinium iodide (IIIf), 1-ethyl-4-hydroxy-1-methyl-3-(p-methylbenzoyl)-4-(p-methylphenyl)piperidinium iodide (IIIg). Toxicity was tested by the brine shrimp bioassay as an intermediate test before further in vivo animal experiments. Piperidine derivatives were found to be more potent than bis Mannich bases. Quaternary piperidine derivatives IIIf and IIIg and also non-quaternary piperidine derivatives IIIb, IIIe, IIIc and IIId were more toxic than 5-fluorouracil in brine shrimp bioassay. Except for IIe, bis Mannich bases were not effective. Quaternization and conversion of bis Mannich bases to corresponding piperidines improved the toxicity. The lipid solubility of the compounds may not affect the toxicity. From these findings the quaternary piperidine derivatives IIIf and IIIg could be used in further drug development and also for in vivo experiments.

  1. Nitrene Metathesis and Catalytic Nitrene Transfer Promoted by Niobium Bis(imido) Complexes.

    PubMed

    Kriegel, Benjamin M; Bergman, Robert G; Arnold, John

    2016-01-13

    We report a metathesis reaction in which a nitrene fragment from an isocyanide ligand is exchanged with a nitrene fragment of an imido ligand in a series of niobium bis(imido) complexes. One of these bis(imido) complexes also promotes nitrene transfer to catalytically generate asymmetric dialkylcarbodiimides from azides and isocyanides in a process involving the Nb(V)/Nb(III) redox couple.

  2. Microwave-promoted synthesis of bicyclic azocine-β-lactams from bis(allenes).

    PubMed

    Alcaide, Benito; Almendros, Pedro; Aragoncillo, Cristina; Fernández, Israel; Gómez-Campillos, Gonzalo

    2014-08-01

    A metal-free preparation of structurally novel bicyclic azocine-β-lactams has been developed. The first examples accounting for the preparation of eight-membered rings from bis(allenes) in the absence of metals have been achieved by the thermolysis of nonconjugated 2-azetidinone-tethered bis(allenes) on application of microwave irradiation. This selective carbocyclization reaction has been studied experimentally, and additionally, its mechanism has been investigated by a DFT study.

  3. The Effect of Fentanyl on Bispectral Index (BIS) Values and Recall

    DTIC Science & Technology

    2002-12-01

    70 may mean deep hypnosis for one patient and moderate sedation with high recall probability for another. There is a gap in the literature with...during general anesthesia for monitoring patients ’ level of hypnosis according to trends in their BIS values. BIS values and the corresponding levels...of primary team in 3 separate live missions) 1998-2000 Staff Nurse, Medical-Surgical Unit, Dover AFB, Delaware Assistant Director of the Patient

  4. Synthesis and murine antineoplastic activity of bis[(carbamoyloxy)methyl] derivatives of pyrrolo[2,1-a]isoquinoline.

    PubMed

    Anderson, W K; McPherson, H L; New, J S; Rick, A C

    1984-10-01

    The synthesis of 4,5-dihydropyrrolo[2,1-a]isoquinolines is reported. A key intermediate in the synthesis of 8-methoxy-4,5-dihydropyrrolo[2,1-a]isoquinolines, 6-hydroxy-1,2,3,4-tetrahydroisoquinoline-1-carboxylic acid (6), was prepared by using a regiospecific phenolic cyclization reaction. The P388 lymphocytic activity is reported for 1,2-bis(hydroxymethyl)-5,6-dihydro-8-methoxy-3-methylpyrrolo [2,1-a]isoquinoline bis(isopropylcarbamate) (11a), 1,2-bis(hydroxymethyl)-5,6-dihydro-8-methoxy-3-methylpyrrolo[2,1-a ]isoquinoline bis(cyclohexylcarbamate) (11b), 1,2-bis(hydroxymethyl)-5,6-dihydro-3-methylpyrrolo[2,1-a]isoqui nol ine bis(methylcarbamate) (13a), 1,2-bis(hydroxymethyl)-5,6-dihydro-3-methylpyrrolo [2,1-a]isoquinoline bis(ethylcarbamate) (13b), and 1,2-bis(hydroxymethyl)-5,6-dihydroxy-3-methylpyrrolo[2,1-a]isoq uin oline bis(cyclohexylcarbamate) (13c); all of the compounds were active. Compound 11a was tested in an expanded tumor panel and was shown to be active against B16 melanocarcinoma, CD8F1 mammary, L1210 lymphoid leukemia, colon 38, and MX-1 human tumor breast xenograft systems.

  5. Reactions of bis[bis(trimethylsilyl)amido] zinc with amides of sulfonimidic acids. Crystal structure and NMR studies of bischelate zinc complex

    NASA Astrophysics Data System (ADS)

    Guzyr, Olexandr I.; Markovskii, Leonid N.; Povolotskii, Mark I.; Roesky, Herbert W.; Chernega, Alexander N.; Rusanov, Eduard B.

    2006-05-01

    Reactions of bis[bis(trimethylsilyl)amido] zinc with amides of sulfonimidic acids are leading to the corresponding bischelate complexes 1- 3. Compounds 1- 3 were characterized by means of NMR spectroscopy and elemental analysis. The X-ray analysis of [ p-MeC 6H 4S(O)(N t-Bu) 2] 2Zn ( 3) demonstrates a tetrahedral environment of the Zn atom in the solid state and dynamic 1H NMR studies showed interconvention between two conformers in solution at high temperatures.

  6. 15 CFR Supplement No. 1 to Part 748 - BIS-748P, BIS-748P-A; Item Appendix, and BIS-748P-B; End-User Appendix; Multipurpose Application...

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... labeled “Export” with an (X). Reexport. If the items are located outside the United States, mark the Box labeled “Reexport” with an (X). Classification. If you are requesting BIS to classify your item against the Commerce Control List (CCL), mark the Box labeled “Classification Request” with an (X)....

  7. Crystal structure of the new hybrid material bis-(1,4-diazo-niabi-cyclo-[2.2.2]octa-ne) di-μ-chlorido-bis-[tetra-chlorido-bis-muthate(III)] dihydrate.

    PubMed

    Chouri, Marwen; Boughzala, Habib

    2015-11-01

    The title compound bis-(1,4-diazo-niabi-cyclo-[2.2.2]octa-ne) di-μ-chlorido-bis-[tetra-chlorido-bis-muthate(III)] dihydrate, (C6H14N2)2[Bi2Cl10]·2H2O, was ob-tain-ed by slow evaporation at room temperature of a hydro-chloric aqueous solution (pH = 1) containing bis-muth(III) nitrate and 1,4-di-aza-bicyclo-[2.2.2]octane (DABCO) in a 1:2 molar ratio. The structure displays a two-dimensional arrangement parallel to (100) of isolated [Bi2Cl10](4-) bi-octa-hedra (site symmetry -1) separated by layers of organic 1,4-diazo-niabi-cyclo-[2.2.2]octane dications [(DABCOH2)(2+)] and water mol-ecules. O-H⋯Cl, N-H⋯O and N-H⋯Cl hydrogen bonds lead to additional cohesion of the structure.

  8. Hydrogen-bonded network structures in dipyridinium, bis­(2-methyl­pyridinium), bis­(3-methyl­pyridinium) and bis­(4-methyl­pyridinium) dioxidobis(oxydiacetato)uranate(VI)

    PubMed Central

    Lennartson, Anders; Håkansson, Mikael

    2010-01-01

    Four complexes containing the [UO2(oda)2]2− anion (oda is oxy­diacetate) are reported, namely dipyridinium dioxidobis(oxydiacetato)uranate(VI), (C5H6N)2[U(C4H4O5)2O2], (I), bis(2-methyl­pyridinium) dioxidobis(oxydiacetato)uranate(VI), (C8H8N)2[U(C4H4O5)2O2], (II), bis­(3-methyl­pyridinium) di­oxido­bis(oxydiacetato)uranate(VI), (C8H8N)2[U(C4H4O5)2O2], (III), and bis­(4-methyl­pyridinium) dioxidobis(oxydiacetato)uranate(VI), (C8H8N)2[U(C4H4O5)2O2], (IV). The anions are achiral and are located on a mirror plane in (I) and on inversion centres in (II)–(IV). The four complexes are assembled into three-dimensional structures via N—H⋯O and C—H⋯O inter­actions. Compounds (III) and (IV) are isomorphous; the [UO2(oda)2]2− anions form a porous matrix which is nearly identical in the two structures, and the cations are located in channels formed in this matrix. Compounds (I) and (II) are very different from (III) and (IV): (I) forms a layered structure, while (II) forms ribbons. PMID:20203398

  9. Synthesis and characterization of the adducts of bis(O-butylxanthato)Ni(II) with nitrogen donor ligands and X-ray structure of bis(O-butylxanthato)bis(3-chloropyridine)nickel(II)

    NASA Astrophysics Data System (ADS)

    Kour, Inderjeet; Kour, Gurvinder; Sachar, Renu; Anthal, Sumati; Kant, Rajni

    2017-01-01

    A new series of adducts of bis(O-butylxanthato)nickel(II) with substituted pyridines have been synthesized by treating bis(O-butylxanthato)nickel(II) with substituted pyridines in acetone. The complexes have been characterized by elemental analysis, conductivity measurements, magnetic susceptibility measurements, TGA/DTA studies, infrared and electronic spectral studies. X-ray studies of one of the adduct bis(O-butylxanthato)bis(3-chloropyridine)nickel(II) shows that the central metal is octahedrally coordinated within a trans-N2S4 donor set, with the Ni atom located on a centre of inversion. The complex crystallizes in the monoclinic space group P21/c with unit cell parameters a = 11.8088(8) Å, b = 12.2042(7) Å, c = 9.0252(5) Å, β = 93.789(6), Z = 2. Crystal structure was solved by direct methods and refined by full matrix least squares procedures to a final R-value of 0.0380 (wR2 = 0.0885) for 2083 observed reflections. The butyl chain is disordered over two set of sites, with occupancy ratios of 0.741:0.259. These studies suggest a distorted octahedral structure and paramagnetic nature of the adducts.

  10. Directed evolution of RuBisCO hypermorphs through genetic selection in engineered E.coli.

    PubMed

    Parikh, Monal R; Greene, Dina N; Woods, Kristen K; Matsumura, Ichiro

    2006-03-01

    The Calvin Cycle is the primary conduit for the fixation of carbon dioxide into the biosphere; ribulose 1,5-bisphosphate carboxylase/oxygenase (RuBisCO) catalyzes the rate-limiting fixation step. Our goal is to direct the evolution of RuBisCO variants with improved kinetic and biophysical properties. The Calvin Cycle was partially reconstructed in Escherichia coli; the engineered strain requires the Synechococcus PCC6301 RuBisCO for growth in minimal media supplemented with a pentose. We randomly mutated the gene encoding the large subunit of RuBisCO (rbcL), co-expressed the resulting library with the small subunit (rbcS) and the Synechococcus PCC7492 phosphoribulokinase (prkA), and selected hypermorphic variants. The RuBisCO variants that evolved during three rounds of random mutagenesis and selection were over-expressed, and exhibited 5-fold improvement in specific activity relative to the wild-type enzyme. These results demonstrate a new strategy for the artificial selection of RuBisCO and other non-native metabolic enzymes.

  11. Chiral stationary phases based on chitosan bis(4-methylphenylcarbamate)-(alkoxyformamide).

    PubMed

    Feng, Zi-Wei; Chen, Wei; Bai, Zheng-Wu

    2016-10-01

    Highly N-deacetylated chitosan was chosen as a natural chiral origin for the synthesis of the selectors of chiral stationary phases. Therefore, chitosan was firstly acylated by various alkyl chloroformates yielding chitosan alkoxyformamides, and then these resulting products were further derivatized with 4-methylphenyl isocyanate to afford chitosan bis(4-methylphenylcarbamate)-(alkoxyformamide). A series of chiral stationary phases was prepared by coating these derivatives on 3-aminopropyl silica gel. The content of the derivatives on the chiral stationary phases was nearly 20% by weight. The chiral stationary phases prepared from chitosan bis(4-methylphenylcarbamate)-(ethoxyformamide) and chitosan bis(4-methylphenylcarbamate)-(isopropoxyformamide) comparatively showed better enantioseparation capability than those prepared from chitosan bis(4-methylphenylcarbamate)-(n-pentoxyformamide) and chitosan bis(4-methylphenylcarbamate)-(benzoxyformamide). The tolerance against organic solvents of the chiral stationary phase of chitosan bis(4-methylphenylcarbamate)-(ethoxyformamide) was investigated, and the results revealed that this phase can work in 100% ethyl acetate and 100% chloroform mobile phases. Because as-synthesized chiral selectors did not dissolve in many common organic solvents, the corresponding chiral stationary phases can be utilized in a wider range of mobile phases in comparison with conventional coating type chiral stationary phases of cellulose and amylose derivatives.

  12. Bis(phosphine)boronium salts. Synthesis, structures and coordination chemistry.

    PubMed

    Shuttleworth, Timothy A; Huertos, Miguel A; Pernik, Indrek; Young, Rowan D; Weller, Andrew S

    2013-09-28

    The synthesis of a range of bis(phosphine)boronium salts is reported [(R2HP)2BH2][X] (R = Ph, (t)Bu, Cy) in which the counter anion is also varied (X(-) = Br(-), [OTf](-), [BAr(F)4](-), Ar(F) = 3,5-(CF3)2C6H3). Characterization in the solid-state by X-ray diffraction suggests there are weak hydrogen bonds between the PH units of the boronium cation and the anion (X(-) = Br(-), [OTf](-)), while solution NMR spectroscopy also reveals hydrogen bonding occurs in the order [BAr(F)4](-) < [OTf](-) < Br(-). [(Ph2HP)2BH2][BAr(F)4] reacts with RhH(PPh3)3, by elimination of H2, forming [Rh(κ(1),η-PPh2BH2·PPh2H)(PPh3)2][BAr(F)4] which shows a β-B-agostic interaction from the resulting base stabilised phosphino-borane ligand. Alternatively such ligands can be assembled directly on the metal centre by reaction of in situ generated {Rh(PPh3)3}(+) and Ph2HP·BH3 to afford [Rh(κ(1),η-PPh2BH2·PPh3)(PPh3)2][BAr(F)4], which was characterised by X-ray crystallography. Addition of H3B·PPh2H to the well-defined 16-electron "T-shaped" complex [Rh(P(i)Bu3)2(PPh3)][BAr(F)4] (characterised by X-ray crystallography) formed of a mixture of base-stabilised phosphino borane ligated complexes [Rh(κ(1),η-PR2BH2·PR3)(PR3)2][BAr(F)4] (R = (i)Bu or Ph). These last observations may lend clues to the formation of bis(phosphine)boronium salts in the catalytic dehydrocoupling reaction of phosphine boranes as mediated by Rh(I) compounds.

  13. Functional materials from self-assembled bis-urea macrocycles.

    PubMed

    Shimizu, Linda S; Salpage, Sahan R; Korous, Arthur A

    2014-07-15

    CONSPECTUS: This Account highlights the work from our laboratories on bis-urea macrocycles constructed from two C-shaped spacers and two urea groups. These simple molecular units assembled with high fidelity into columnar structures guided by the three-centered urea hydrogen bonding motif and aryl stacking interactions. Individual columns are aligned and closely packed together to afford functional and homogeneous microporous crystals. This approach allows for precise and rational control over the dimensions of the columnar structure simply by changing the small molecular unit. When the macrocyclic unit lacks a cavity, columnar assembly gives strong pillars. Strong pillars with external functional groups such as basic lone pairs can expand like clays to accept guests between the pillars. Macrocycles that contain sizable interior cavities assemble into porous molecular crystals with aligned, well-defined columnar pores that are accessible to gases and guests. Herein, we examine the optimal design of the macrocyclic unit that leads to columnar assembly in high fidelity and probe the feasibility of incorporating a second functional group within the macrocycles. The porous molecular crystals prepared through the self-assembly of bis-urea macrocycles display surface areas similar to zeolites but lower than MOFs. Their simple one-dimensional channels are well-suited for studying binding, investigating transport, diffusion and exchange, and monitoring the effects of encapsulation on reaction mechanism and product distribution. Guests that complement the size, shape, and polarity of the channels can be absorbed into these porous crystals with repeatable stoichiometry to form solid host-guest complexes. Heating or extraction with an organic solvent enables desorption or removal of the guest and subsequent recovery of the solid host. Further, these porous crystals can be used as containers for the selective [2 + 2] cycloadditions of small enones such as 2-cyclohexenone or 3

  14. Air-stable platinum and palladium complexes featuring bis[2,4-bis(trifluoromethyl)phenyl]phosphinous acid ligands.

    PubMed

    Kurscheid, Boris; Neumann, Beate; Stammler, Hans-Georg; Hoge, Berthold

    2011-12-23

    Secondary phosphane oxides, R(2)P(O)H, are commonly used as preligands for transition-metal complexes of phosphinous acids, R(2)P-OH (R=alkyl, aryl), which are relevant as efficient catalysts in cross-coupling processes. In contrast to previous work by other groups, we are interested in the ligating properties of an electron-deficient phosphinous acid, (R(f))(2)P-OH, bearing the strongly electron-withdrawing and sterically demanding 2,4-bis(trifluoromethyl)phenyl group towards catalysis-relevant metals, such as palladium and platinum. The preligand bis[2,4-bis(trifluoromethyl)phenyl]phosphane oxide, (R(f))(2)P(O)H, reacts smoothly with solid platinum(II) dichloride yielding the trans-configured phosphinous acid platinum complex trans-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)]. The deprotonation of one phosphinous acid ligand with an appropriate base leads to the cis-configured monoanion complex cis-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H](-), featuring the quasi-chelating phosphinous acid phosphinito unit, (R(f))(2)P-O-H···O=P(R(f))(2), which exhibits a strong hydrogen bridge substantiated by an O···O distance of 245.1(4) pm. The second deprotonation step is accompanied by a rearrangement to afford the trans-configured dianion trans-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)](2-). The reaction of (R(f))(2)P(O)H with solid palladium(II) dichloride initially yields a mononuclear palladium complex [PdCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)], which condenses under liberation of HCl to the neutral dinuclear palladium complex [Pd(2)(μ-Cl)(2){({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H}(2)]. The equilibrium between the mononuclear [PdCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)] and dinuclear [Pd(2)(μ-Cl)(2){({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H}(2)] palladium complexes is reversible and can be shifted in each direction by the addition of base or HCl, respectively. Treatment of palladium(II) hexafluoroacetylacetonate, [Pd(F(6)acac)(2)], with a slight excess of (R(f))(2)P

  15. Contemporary carbon content of bis (2-ethylhexyl) phthalate in butter.

    PubMed

    Tong, T; Ondov, J M; Buchholz, B A; VanDerveer, M C

    2016-01-01

    The fraction of naturally produced bis (2-ethylhexyl) phthalate (DEHP), a ubiquitous plasticizer known to contaminate packaged foods, was determined for each of five 1.10 kg samples of unsalted market butter by accelerator mass spectrometry (AMS). After extraction and concentration enrichment with liquid-liquid extraction, flash column chromatography, and preparative-scale high performance liquid chromatography, each sample provided ≈ 250 μg extracts of DEHP with carbon purity ranging from 92.5 ± 1.2% (n = 3, 1σ) to 97.1 ± 0.8% (n = 3, 1σ) as measured with gas chromatography mass spectrometry (GC-MS). After corrections for method blank DEHP, co-eluting compounds, and unidentified carbon, the mean fraction of naturally produced DEHP in butter was determined to be 0.16 ± 0.12 (n = 5, 1σ). To our knowledge, this is the first report of the contemporary fraction of DEHP isolated from market butter in the U.S.

  16. Bis(porphyrin)-anthraquinone triads: synthesis, spectroscopy, and photochemistry.

    PubMed

    Giribabu, L; Reeta, P Silviya; Kanaparthi, Ravi Kumar; Srikanth, Malladi; Soujanya, Y

    2013-04-11

    Molecular triads based on bis(porphyrin)-anthraquinone having azomethine bridge at the pyrrole-β position have been designed and synthesized. Both free-base AQ-(H2)2 and zinc AQ-(Zn)2 triads are characterized by elemental analysis, MALDI-MS, (1)H NMR, UV-visible, and fluorescence spectroscopy (steady-state and time-resolved) as well as electrochemical method. The absorption spectra of both Soret and Q-bands of the triads are red-shifted by 12-20 nm with respect to their monomer units. The study supported by theoretical calculations manifests that there exists a negligible electronic communication in the ground state between the donor porphyrin and acceptor anthraquinone of these triads. However, interestingly, both the triads exhibit significant fluorescence emission quenching (51-92%) of the porphyrin emission compared to their monomeric units. The emission quenching is attributed to the excited-state intramolecular photoinduced electron transfer from porphyrins to anthraquinone. The electron-transfer rates (kET) of these triads are found in the range 1.0 × 10(8) to 7.7 × 10(9) s(-1) and are found to be solvent dependent.

  17. Mono- and bis-tolylterpyridine iridium(III) complexes

    SciTech Connect

    Hinkle, Lindsay M.; Young, Jr., Victor G.; Mann, Kent R.

    2012-01-20

    The first structure report of trichlorido[4'-(p-tolyl)-2,2':6',2{double_prime}-terpyridine]iridium(III) dimethyl sulfoxide solvate, [IrCl{sub 3}(C{sub 22}H{sub 17}N{sub 3})] {center_dot} C{sub 2}H{sub 6}OS, (I), is presented, along with a higher-symmetry setting of previously reported bis[4'-(p-tolyl)-2,2':6',2{double_prime}-terpyridine]iridium(III) tris(hexafluoridophosphate) acetonitrile disolvate, [Ir(C{sub 22}H{sub 17}N{sub 3})2](PF{sub 6}){sub 3} {center_dot} 2C{sub 2}H{sub 3}N, (II) [Yoshikawa, Yamabe, Kanehisa, Kai, Takashima & Tsukahara (2007). Eur. J. Inorg. Chem. pp. 1911-1919]. For (I), the data were collected with synchrotron radiation and the dimethyl sulfoxide solvent molecule is disordered over three positions, one of which is an inversion center. The previously reported structure of (II) is presented in the more appropriate C2/c space group. The iridium complex and one PF{sub 6}{sup -} anion lie on twofold axes in this structure, making half of the molecule unique.

  18. Contemporary Carbon Content of Bis (2-ethylhexyl) Phthalate in Butter

    PubMed Central

    Tong, T.; Ondov, J. M.; Buchholz, B. A.; VanDerveer, M. C.

    2016-01-01

    The fraction of naturally produced Bis (2-ethylhexyl) phthalate (DEHP), a ubiquitous plasticizer known to contaminate packaged foods, was determined for each of five 1.10 kg samples of unsalted market butter by accelerator mass spectrometry (AMS). After extraction and concentration enrichment with liquid-liquid extraction, flash column chromatography, and preparative-scale high performance liquid chromatography, each sample provided ≈250 µg extracts of DEHP with carbon purity ranging from 92.5±1.2% (n=3, 1σ) to 97.1±0.8% (n=3, 1σ) as measured with gas chromatography mass spectrometry (GC-MS). After corrections for method blank DEHP, co-eluting compounds, and unidentified carbon, the mean fraction of naturally produced DEHP in butter was determined to be 0.16±0.12 (n=5, 1σ). To our knowledge, this is the first report of the contemporary fraction of DEHP isolated from market butter in the U.S. PMID:26213077

  19. Synthesis and properties of disodium tetraethyleneglycol-bis-(alpha-carboxybenzylpenicillin).

    PubMed

    Kim, Y T; Jung, Y J; Kim, Y M

    1999-04-01

    Disodium tetraethyleneglycol-bis-(alpha-carboxybenzylpenicillin) (TEG-carbenicillin), a tetraethyleneglycol (TEG) diester of carbenicillin, was synthesized to develop a carbenicillin prodrug with enhanced acid stability for oral administration. Antimicrobial activities of TEG-carbenicillin tested against gram-negative Escherichia coli (TG-1) and gram-positive Staphylococcus aureus (ATCC-12228) and Bacillus subtilis (NA-1) were comparable to that of carbenicillin. Stability of the beta-lactam ring of TEG-carbenicillin was determined by iodometry at pH 6.8, pH 4.5, and pH 2.0 at varied time intervals and was compared to that of carbenicillin. In 26 hr, both of the compounds were stable at pH 6.8. At pH 4.5, about 41% of the carbenicillin was decomposed, while TEG-carbenicillin was not appreciably decomposed. At pH 2.0, carbenicillin was decomposed about 61% after 6 hr, while TEG-carbenicillin was decomposed about 21% during the same period.

  20. Synthesis, Radiolabeling, and Bioevaluation of Bis(Trifluoromethanesulfonyl) Imide.

    PubMed

    Ersöz, Onur Alp; Soylu, Hale Melis; Er, Ozge; Ocakoglu, Kasim; Lambrecht, Fatma Yurt; Yilmaz, Osman

    2015-11-01

    Imidazolium salts have antitumor potential and toxicological effects on various microorganisms. The authors' aim is to synthesize a new imidazolium salt and to assess its pharmacokinetic and antitumor potentials by in vitro and in vivo studies. In this study, bis(trifluoromethanesulfonyl) imide (ITFSI) was synthesized and labeled with (131)I using the iodogen method. The efficiency of radiolabeling was determined with high yield (95.5% ± 3.7%). Pharmacokinetic properties of the compound were investigated in albino Wistar rats using radiolabeled compound. The radiolabeled compound ((131)I-ITFSI) has been stable during a period of 3 hours in human serum. The uptake of (131)I-ITFSI reached maximum in the spleen, liver, and blood at 60 minutes, large intestine and heart at 30 minutes, and ovary at 120 minutes. It is observed that intracellular uptake of the radiolabeled compound is higher in the CaCo-2 (colon adenocarcinoma tumor) cell line than HEK-293 (human epithelial kidney) cell line. In further study, antitumor potential of ITFSI on a colon adenocarcinoma tumor-bearing animal model may be investigated.

  1. Quantum chemical computational studies on bis-thiourea zinc acetate

    NASA Astrophysics Data System (ADS)

    Pir, Hacer; Günay, Nergin; Tamer, Ömer; Avci, Davut; Tarcan, Erdoğan; Atalay, Yusuf

    2013-08-01

    In this study, quantum chemical calculations of vibrational spectra, Raman spectra, electronic properties (total energy, dipole moment, electronegativity, chemical hardness and softness), Mulliken atomic charges and thermodynamic parameters of bis-thiourea zinc acetate (BTZA) have been performed using Gaussian 09 program. Additionally, nonlinear optical (NLO), conformational, natural bond orbital (NBO) analyses of BTZA have been carried out using the same program. The structural and spectroscopic data of the molecule in the ground state have been calculated using Hartree-Fock (HF) and density functional method (DFT/B3LYP) with the 6-311++G(d,p) basis set. In addition, the molecular frontier orbital energies (HOMO, HOMO-1, LUMO and LUMO+1) of the title compound have been calculated at the HF and B3LYP levels. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. Finally, the calculated results were applied to simulate infrared and Raman spectra of the title compound which showed good agreement with the experimental ones.

  2. High-temperature polyimides prepared from 2,2-bis-[(2-halo-4-aminophenoxy)-phenyl]hexafluoropropane

    NASA Technical Reports Server (NTRS)

    Jones, Robert J. (Inventor); Chang, Glenn E. C. (Inventor)

    1984-01-01

    There are provided the aromatic diamines 2,2-bis-[(2-halo-4-aminophenoxy)-phenyl]hexafluoropropane, where the attached ortho halogen is preferably chlorine, and 4,4'-bis(4-aminophenoxy)biphenyl, as novel monomers for polyimide polymerizations. The former, when reacted with 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, provides a polyimide having exceptional high-temperature performance. The latter diamine is a low-cost monomer for polyimide production.

  3. Hexaaquacobalt(II) and hexaaquanickel(II) bis(μ-pyridine-2,6-dicarboxylato)bis[(pyridine-2,6-dicarboxylato)bismuthate(III)] dihydrate.

    PubMed

    Stavila, Vitalie; Bulimestru, Ion; Gulea, Aurelian; Colson, Adam C; Whitmire, Kenton H

    2011-03-01

    The title complexes, hexaaquacobalt(II) bis(μ-pyridine-2,6-dicarboxylato)bis[(pyridine-2,6-dicarboxylato)bismuthate(III)] dihydrate, [Co(H(2)O)(6)][Bi(2)(C(7)H(4)NO(4))(4)]·2H(2)O, (I), and hexaaquanickel(II) bis(μ-pyridine-2,6-dicarboxylato)bis[(pyridine-2,6-dicarboxylato)bismuthate(III)] dihydrate, [Ni(H(2)O)(6)][Bi(2)(C(7)H(4)NO(4))(4)]·2H(2)O, (II), are isomorphous and crystallize in the triclinic space group P-1. The transition metal ions are located on the inversion centre and adopt slightly distorted MO(6) (M = Co or Ni) octahedral geometries. Two [Bi(pydc)(2)](-) units (pydc is pyridine-2,6-dicarboxylate) are linked via bridging carboxylate groups into centrosymmetric [Bi(2)(pydc)(4)](2-) dianions. The crystal packing reveals that the [M(H(2)O)(6)](2+) cations, [Bi(2)(pydc)(4)](2-) anions and solvent water molecules form multiple hydrogen bonds to generate a supramolecular three-dimensional network. The formation of secondary Bi...O bonds between adjacent [Bi(2)(pydc)(4)](2-) dimers provides an additional supramolecular synthon that directs and facilitates the crystal packing of both (I) and (II).

  4. Crystal structures of the water and acetone monosolvates of bis-[4'-(pyridin-4-yl)-2,2':6',2''-terpyridine]-manganese(II) bis-(hexa-fluorido-phosphate).

    PubMed

    Lourenço, Leandro M O; Almeida Paz, Filipe A; Fernandes, José A

    2015-04-01

    The crystal structures of bis-[4'-(pyridin-4-yl)-2,2':6',2''-terpyridine]-man-gan-ese(II) bis-(hexa-fluorido-phosphate) monohydrate, [Mn(C20H14N4)2](PF6)2·H2O, (1), and bis-[4'-(pyridin-4-yl)-2,2':6',2''-terpyridine]-manganese(II) bis(hexa-fluorido-phosphate) acetone monosolvate, (2), [Mn(C20H14N4)2](PF6)2·CH3COCH3, are described. At 150 K, (1) and (2) have monoclinic (P21/c) and ortho-rhom-bic (C2221) symmetries, respectively. Both structures exhibit octahedrally coordinated Mn(II) atoms and disorder. They display weak inter-actions, such as C-H⋯F, C-H⋯N, C-H⋯π, F⋯π and π-π. The twofold rotation axis in the molecule of (2) is coincident with a twofold rotation axis of the crystal.

  5. Design, Synthesis, and X-ray Structure of Substituted Bis-tetrahydrofuran (Bis-THF)-Derived Potent HIV-1 Protease Inhibitors

    SciTech Connect

    Ghosh, Arun K.; Martyr, Cuthbert D.; Steffey, Melinda; Wang, Yuan-Fang; Agniswamy, Johnson; Amano, Masayuki; Weber, Irene T.; Mitsuya, Hiroaki

    2012-06-18

    We investigated substituted bis-THF-derived HIV-1 protease inhibitors in order to enhance ligand-binding site interactions in the HIV-1 protease active site. In this context, we have carried out convenient syntheses of optically active bis-THF and C4-substituted bis-THF ligands using a [2,3]-sigmatropic rearrangement as the key step. The synthesis provided convenient access to a number of substituted bis-THF derivatives. Incorporation of these ligands led to a series of potent HIV-1 protease inhibitors. Inhibitor 23c turned out to be the most potent (K{sub i} = 2.9 pM; IC{sub 50} = 2.4 nM) among the inhibitors. An X-ray structure of 23c-bound HIV-1 protease showed extensive interactions of the inhibitor with the protease active site, including a unique water-mediated hydrogen bond to the Gly-48 amide NH in the S2 site.

  6. Potent inhibition of scrapie prion replication in cultured cells by bis-acridines

    PubMed Central

    May, Barnaby C. H.; Fafarman, Aaron T.; Hong, Septima B.; Rogers, Michael; Deady, Leslie W.; Prusiner, Stanley B.; Cohen, Fred E.

    2003-01-01

    Prion diseases are characterized by an accumulation of PrPSc, a misfolded isoform of the normal cellular prion protein, PrPC. We previously reported the bioactivity of acridine-based compounds against PrPSc replication in scrapie-infected neuroblastoma cells and now report the improved potency of bis-acridine compounds. Bis-acridines are characterized by a dimeric motif, comprising two acridine heterocycles tethered by a linker. A library of bis-(6-chloro-2-methoxy-acridin-9-yl) and bis-(7-chloro-2-methoxy-benzo[b][1,5]naphthyridin-10-yl) analogs was synthesized to explore the effect of structurally diverse linkers on PrPSc replication in scrapie-infected neuroblastoma cells. Structure–activity analysis revealed that linker length and structure are important determinants for inhibition of prion replication in cultured scrapied cells. Three bis-acridine analogs, (6-chloro-2-methoxy-acridin-9-yl)-(3-{4-[3-(6-chloro-2-methoxy-acridin-9-ylamino)-propyl]-piperazin-1-yl}-propyl)-amine, N,N′-bis-(6-chloro-2-methoxy-acridin-9-yl)-1,8-diamino-3,6-dioxaoctane, and (1-{[4-(6-chloro-2-methoxy-acridin-9-ylamino)-butyl]-[3-(6-chloro-2-methoxy-acridin-9-ylamino)-propyl]-carbamoyl}-ethyl)-carbamic acid tert-butyl ester, showed half-maximal inhibition of PrPSc formation at 40, 25, and 30 nM, respectively, and were not cytotoxic to uninfected neuroblastoma cells at concentrations of 500 nM. Our data suggest that bis-acridine analogs may provide a potent alternative to the acridine-based compound quinacrine, which is currently under clinical evaluation for the treatment of prion disease. PMID:12626750

  7. In silico Identification of Ergosterol as a Novel Fungal Metabolite Enhancing RuBisCO Activity in Lycopersicum esculentum.

    PubMed

    Mitra, Joyeeta; Narad, Priyanka; Sengupta, Abhishek; Sharma, P D; Paul, P K

    2016-09-01

    RuBisCO (EC 4.1.1.39), a key enzyme found in stroma of chloroplast, is important for fixing atmospheric CO2 in plants. Alterations in the activity of RuBisCO could influence photosynthetic yield. Therefore, to understand the activity of the protein, knowledge about its structure is pertinent. Though the structure of Nicotiana RuBisCO has been modeled, the structure of tomato RuBisCO is still unknown. RuBisCO extracted from chloroplasts of tomato leaves was subjected to MALDI-TOF-TOF followed by Mascot Search. The protein sequence based on gene identification numbers was subjected to in silico model construction, characterization and docking studies. The primary structure analysis revealed that protein was stable, neutral, hydrophilic and has an acidic pI. The result though indicates a 90 % homology with other members of Solanaceae but differs from the structure of Arabidopsis RuBisCO. Different ligands were docked to assess the activity of RuBisCO against these metabolite components. Out of the number of modulators tested, ergosterol had the maximum affinity (E = -248.08) with RuBisCO. Ergosterol is a major cell wall component of fungi and has not been reported to be naturally found in plants. It is a known immune elicitor in plants. The current study throws light on its role in affecting RuBisCO activity in plants, thereby bringing changes in the photosynthetic rate.

  8. Silicon-containing bis-azomethines: Synthesis, structural characterization, evaluation of the photophysical properties and biological activity

    NASA Astrophysics Data System (ADS)

    Zaltariov, Mirela-Fernanada; Vlad, Angelica; Cazacu, Maria; Avadanei, Mihaela; Vornicu, Nicoleta; Balan, Mihaela; Shova, Sergiu

    2015-03-01

    A new diamine, (dimethylsilanediyl)bis(methylene)bis(4-aminobenzoate) (1), containing dimethylsilane spacer, was prepared by the condensation of p-aminobenzoic acid with bis(chloromethyl)dimethylsilane. This was subsequently reacted with salicylaldehyde, 3-hydroxy-salicylaldehyde, and 3-methoxy-salicyladehyde, when corresponding Schiff bases (E)-(dimethylsilanediyl)bis(methylene)bis(4-((E)-(2-hydroxybenzilidene)amino)benzoate (2), (E)-(dimethylsilanediyl)bis(methylene)bis(4-((E)-(2-hydroxybenzilidene)amino)benzoate (3), and (E)-(dimethylsilanediyl)bis(methylene) bis(4-((E)-(2-hydroxy-3-methoxybenzilidene)amino)benzoate (4), respectively were formed. All the obtained compounds were structurally characterized by spectral (FT-IR, 1HNMR, 13CNMR) analyses and single crystal X-ray diffraction. Photophysical studies revealed that the new prepared Schiff bases are good UV light absorbing and fluorescent materials. Thus, they exhibit strong UV/Vis-absorption at 250-400 nm and violet or orange emission, in sensitive dependence on the polarity of the solvents and the nature of the substituent (sbnd H, sbnd OH and sbnd OCH3) at the aromatic ring. The antimicrobial activity of these compounds was first studied in vitro by the disk diffusion assay against two species of bacteria and three fungi. The minimum inhibitory concentration was then determined with the reference of standard compounds. The results displayed that Schiff bases 3 and 4 having hydroxy- and methoxy-substituents on the aromatic ring were better inhibitors of both types of species (bacteria and fungi) than standard compounds, Caspofungin and Kanamycin.

  9. Bis-butanediol-mercapturic acid (bis-BDMA) as a urinary biomarker of metabolic activation of butadiene to its ultimate carcinogenic species.

    PubMed

    Kotapati, Srikanth; Sangaraju, Dewakar; Esades, Amanda; Hallberg, Lance; Walker, Vernon E; Swenberg, James A; Tretyakova, Natalia Y

    2014-06-01

    Human carcinogen 1,3-butadiene (BD) undergoes metabolic activation to 3,4-epoxy-1-butene (EB), hydroxymethylvinyl ketone (HMVK), 3,4-epoxy-1,2-butanediol (EBD) and 1,2,3,4-diepoxybutane (DEB). Among these, DEB is by far the most genotoxic metabolite and is considered the ultimate carcinogenic species of BD. We have shown previously that BD-exposed laboratory mice form 8- to 10-fold more DEB-DNA adducts than rats exposed at the same conditions, which may be responsible for the enhanced sensitivity of mice to BD-mediated cancer. In the present study, we have identified 1,4-bis-(N-acetyl-L-cystein-S-yl)butane-2,3-diol (bis-BDMA) as a novel DEB-specific urinary biomarker. Isotope dilution high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry was employed to quantify bis-BDMA and three other BD-mercapturic acids, 2-(N-acetyl-L-cystein-S-yl)-1-hydroxybut-3-ene/1-(N-acetyl-L-cystein-S-yl)-2-hydroxy-but-3-ene (MHBMA, from EB), 4-(N-acetyl-L-cystein-S-yl)-1,2-dihydroxybutane (DHBMA, from HMVK) and 4-(N-acetyl-L-cystein-S-yl)-1,2,3-trihydroxybutane (THBMA, from EBD), in urine of confirmed smokers, occupationally exposed workers and BD-exposed laboratory rats. Bis-BDMA was formed in a dose-dependent manner in urine of rats exposed to 0-200 p.p.m. BD by inhalation, although it was a minor metabolite (1%) as compared with DHBMA (47%) and THBMA (37%). In humans, DHBMA was the most abundant BD-mercapturic acid excreted (93%), followed by THBMA (5%) and MHBMA (2%), whereas no bis-BDMA was detected. These results reveal significant differences in metabolism of BD between rats and humans.

  10. Two novel 3D copper(II) complexes based on a rigid bis-pyridyl-bis-amide and two polycarboxylates mixed ligands: Assembly, structures and properties

    NASA Astrophysics Data System (ADS)

    Wang, Xiu-Li; Mu, Bao; Lin, Hong-Yan; Yang, Song; Liu, Guo-Cheng

    2013-03-01

    Two novel three-dimensional (3D) copper(II) complexes [Cu3(3-bpcb)(1,2-BDC)2(μ2-OH)2] (1) and [Cu2(3-bpcb)1.5(SIP)(μ3-OH)]·H2O (2), based on a rigid bis-pyridyl-bis-amide ligand [3-bpcb = N,N'-bis(3-pyridinecarboxamide)-1,4-benzene] and two different polycarboxylates [1,2-H2BDC = 1,2-benzenedicarboxylic acid, NaH2SIP = sodium 5-sulfoisophthalic acid] have been prepared under hydrothermal conditions. Single crystal X-ray diffraction analysis shows that complex 1 exhibits a 4-nodal mixed (3,4,4,5)-connected 3D structure with the (3·4·5)2(3·42·5·86)2(32·8·92·10)(42·82·102) Schläfli symbol, which is constructed from two-dimensional (2D) Cu(II)-μ2-OH-3-bpcb layers (3-bpcb: μ4-bridging coordination mode via two pyridyl nitrogen and two carbonyl oxygen atoms) and the 1,2-BDC bridging ligands. Complex 2 is also a 3D coordination polymer constructed from the μ2-bridging 3-bpcb ligands (via two pyridyl nitrogen atoms) and the 2D Cu(II)-μ3-OH-SIP sheets containing tetranuclear copper clusters, showing a novel 3-nodal (5,6,6)-connected (33·43·53·63·72·8)(33·43·53·6)(33·46·54·62) topology. The differences between the final 3D structures for complexes 1 and 2 might be attributed to the different aromatic polycarboxylates and the bis-pyridyl-bis-amide ligand with different coordination modes. Moreover, the electrochemical behavior of complex 1 and the fluorescence properties of the complexes 1-2 have been investigated.

  11. New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis.

    PubMed

    Huang, Daria L; Beltrán-Suito, Rodrigo; Thomsen, Julianne M; Hashmi, Sara M; Materna, Kelly L; Sheehan, Stafford W; Mercado, Brandon Q; Brudvig, Gary W; Crabtree, Robert H

    2016-03-07

    This paper introduces Ir(I)(CO)2(pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*Ir(III)(pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO4 results in formation of a blue Ir(IV) species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation process requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting Ir(IV) species. The species formed from oxidation of the Ir(CO)2(pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO)2(pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By (1)H NMR, activated Ir(CO)2(pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3.

  12. Monitoring sleep depth: analysis of bispectral index (BIS) based on polysomnographic recordings and sleep deprivation.

    PubMed

    Giménez, Sandra; Romero, Sergio; Alonso, Joan Francesc; Mañanas, Miguel Ángel; Pujol, Anna; Baxarias, Pilar; Antonijoan, Rosa Maria

    2017-02-01

    The assessment and management of sleep are increasingly recommended in the clinical practice. Polysomnography (PSG) is considered the gold standard test to monitor sleep objectively, but some practical and technical constraints exist due to environmental and patient considerations. Bispectral index (BIS) monitoring is commonly used in clinical practice for guiding anesthetic administration and provides an index based on relationships between EEG components. Due to similarities in EEG synchronization between anesthesia and sleep, several studies have assessed BIS as a sleep monitor with contradictory results. The aim of this study was to evaluate objectively both the feasibility and reliability of BIS for sleep monitoring through a robust methodology, which included full PSG recordings at a baseline situation and after 40 h of sleep deprivation. Results confirmed that the BIS index was highly correlated with the hypnogram (0.89 ± 0.02), showing a progressive decrease as sleep deepened, and an increase during REM sleep (awake: 91.77 ± 8.42; stage N1: 83.95 ± 11.05; stage N2: 71.71 ± 11.99; stage N3: 42.41 ± 9.14; REM: 80.11 ± 8.73). Mean and median BIS values were lower in the post-deprivation night than in the baseline night, showing statistical differences for the slow wave sleep (baseline: 42.41 ± 9.14 vs. post-deprivation: 39.49 ± 10.27; p = 0.02). BIS scores were able to discriminate properly between deep (N3) and light (N1, N2) sleep. BIS values during REM overlapped those of other sleep stages, although EMG activity provided by the BIS monitor could help to identify REM sleep if needed. In conclusion, BIS monitors could provide a useful measure of sleep depth in especially particular situations such as intensive care units, and they could be used as an alternative for sleep monitoring in order to reduce PSG-derived costs and to increase capacity in ambulatory care.

  13. Decomposition of reactive oxygen species by copper(II) bis(1-pyrazolyl)methane complexes.

    PubMed

    Schepetkin, Igor; Potapov, Andrei; Khlebnikov, Andrei; Korotkova, Elena; Lukina, Anna; Malovichko, Galina; Kirpotina, Lilia; Quinn, Mark T

    2006-06-01

    Two bis(1-pyrazolyl)alkane ligands, bis(3,5-dimethyl-1-pyrazolyl)methane and bis(4-iodo-3,5-dimethyl-1-pyrazolyl)methane, and their copper(II) complexes, bis(3,5-dimethyl-1-pyrazolyl)methanedinitratocopper(II) [CuL1(NO3)2] and bis(4-iodo-3,5-dimethyl-1-pyrazolyl)methanedinitratocopper(II) [CuL2(NO3)2] x 2H2O, were prepared. Physiochemical properties of the copper(II) complexes were studied by spectroscopic (UV-vis, IR, EPR) techniques and cyclic voltammetry. Spectroscopic analysis revealed a 1:1 stoichiometry of ligand:copper(II) ion and a bidentate coordination mode for the nitrate ions in both of the complexes. According to experimental and theoretical ab initio data, the copper(II) ion is located in an octahedral hexacoordinated environment. Both complexes were able to catalyze the dismutation of superoxide anion (O2*-) (pH 7.5) and decomposition of H2O2 (pH 7.5) and peroxynitrite (pH 10.9). In addition, both complexes exhibited superoxide dismutase (SOD) like activity toward extracellular and intracellular reactive oxygen species produced by activated human neutrophils in whole blood. Thus, these complexes represent useful SOD mimetics with a broad range of antioxidant activity toward a variety of reactive oxidants.

  14. Chemical bath deposition of Cu3BiS3 thin films

    NASA Astrophysics Data System (ADS)

    Deshmukh S., G.; Panchal A., K.; Vipul, Kheraj

    2016-05-01

    First time, copper bismuth sulfide (Cu3BiS3) thin films were synthesized on the glass substrate using simple, low-cost chemical bath deposition (CBD) technique. The synthesized parameters such as temperature of bath, pH and concentration of precursors were optimized for the deposition of uniform, well adherent Cu3BiS3 thin films. The optical, surface morphology and structural properties of the Cu3BiS3 thin films were studied using UV-VIS-NIR spectra, scanning electron microscopy (SEM) and X-ray diffraction (XRD). The as- synthesized Cu3BiS3 film exhibits a direct band gap 1.56 to 1.58 eV having absorption coefficient of the order of 105 cm-1. The XRD declares the amorphous nature of the films. SEM images shows films were composed of close-packed fine spherical nanoparticles of 70-80 nm in diameter. The chemical composition of the film was almost stoichiometric. The optical study indicates that the Cu3BiS3 films can be applied as an absorber layer for thin film solar cells.

  15. Structural mechanism of RuBisCO activation by carbamylation of the active site lysine.

    PubMed

    Stec, Boguslaw

    2012-11-13

    Ribulose 1,5-bisphosphate carboxylase/oxygenase (RuBisCO) is a crucial enzyme in carbon fixation and the most abundant protein on earth. It has been studied extensively by biochemical and structural methods; however, the most essential activation step has not yet been described. Here, we describe the mechanistic details of Lys carbamylation that leads to RuBisCO activation by atmospheric CO(2). We report two crystal structures of nitrosylated RuBisCO from the red algae Galdieria sulphuraria with O(2) and CO(2) bound at the active site. G. sulphuraria RuBisCO is inhibited by cysteine nitrosylation that results in trapping of these gaseous ligands. The structure with CO(2) defines an elusive, preactivation complex that contains a metal cation Mg(2+) surrounded by three H(2)O/OH molecules. Both structures suggest the mechanism for discriminating gaseous ligands by their quadrupole electric moments. We describe conformational changes that allow for intermittent binding of the metal ion required for activation. On the basis of these structures we propose the individual steps of the activation mechanism. Knowledge of all these elements is indispensable for engineering RuBisCO into a more efficient enzyme for crop enhancement or as a remedy to global warming.

  16. Depletion of abundant plant RuBisCO protein using the protamine sulfate precipitation method.

    PubMed

    Kim, Yu Ji; Lee, Hye Min; Wang, Yiming; Wu, Jingni; Kim, Sang Gon; Kang, Kyu Young; Park, Ki Hun; Kim, Yong Chul; Choi, In Soo; Agrawal, Ganesh Kumar; Rakwal, Randeep; Kim, Sun Tae

    2013-07-01

    Ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO) is the most abundant plant leaf protein, hampering deep analysis of the leaf proteome. Here, we describe a novel protamine sulfate precipitation (PSP) method for the depletion of RuBisCO. For this purpose, soybean leaf total proteins were extracted using Tris-Mg/NP-40 extraction buffer. Obtained clear supernatant was subjected to the PSP method, followed by 13% SDS-PAGE analysis of total, PS-supernatant and -precipitation derived protein samples. In a dose-dependent experiment, 0.1% w/v PS was found to be sufficient for precipitating RuBisCO large and small subunits (LSU and SSU). Western blot analysis confirmed no detection of RuBisCO LSU in the PS-supernatant proteins. Application of this method to Arabidopsis, rice, and maize leaf proteins revealed results similar to soybean. Furthermore, 2DE analyses of PS-treated soybean leaf displayed enriched protein profile for the protein sample derived from the PS-supernatant than total proteins. Some enriched 2D spots were subjected to MALDI-TOF-TOF analysis and were successfully assigned for their protein identity. Hence, the PSP method is: (i) simple, fast, economical, and reproducible for RuBisCO precipitation from the plant leaf sample; (ii) applicable to both dicot and monocot plants; and (iii) suitable for downstream proteomics analysis.

  17. Hybrid Intelligent System to Perform Fault Detection on BIS Sensor During Surgeries.

    PubMed

    Casteleiro-Roca, José-Luis; Calvo-Rolle, José Luis; Méndez Pérez, Juan Albino; Roqueñí Gutiérrez, Nieves; de Cos Juez, Francisco Javier

    2017-01-18

    This paper presents a new fault detection system in hypnotic sensors used for general anesthesia during surgery. Drug infusion during surgery is based on information received from patient monitoring devices; accordingly, faults in sensor devices can put patient safety at risk. Our research offers a solution to cope with these undesirable scenarios. We focus on the anesthesia process using intravenous propofol as the hypnotic drug and employing a Bispectral Index (BIS(TM)) monitor to estimate the patient's unconsciousness level. The method developed identifies BIS episodes affected by disturbances during surgery with null clinical value. Thus, the clinician-or the automatic controller-will not take those measures into account to calculate the drug dose. Our method compares the measured BIS signal with expected behavior predicted by the propofol dose provider and the electromyogram (EMG) signal. For the prediction of the BIS signal, a model based on a hybrid intelligent system architecture has been created. The model uses clustering combined with regression techniques. To validate its accuracy, a dataset taken during surgeries with general anesthesia was used. The proposed fault detection method for BIS sensor measures has also been verified using data from real cases. The obtained results prove the method's effectiveness.

  18. Development of molecular photoswitch with very fast photoresponse based on asymmetrical bis-azospiropyran

    NASA Astrophysics Data System (ADS)

    Nourmohammadian, Farahnaz; Abdi, Ali Ashtiani

    2016-01-01

    To study the effects of an extended bis-azo conjugated bridge with two different photochemical functions on a molecule in photochromic responses, a novel asymmetrical bifunctional bis-azo spiropyran photochromic dye was designed and synthesized. The obtained photoresponses were compared with symmetrical bifunctional bis-azo spiropyran analogues, and relative mono-azo and simple spiropyrans. Colourimetric behaviour, luminescence, and switching kinetics of all the dyes were studied. The largest molar absorption coefficient in merocyanine form, quickest response to light, and highest fluorescence quantum yield of the spiropyran form with a superior ratio of emission intensities of spiropyran to merocyanine form were achieved for the asymmetric bis-azospiropyran. Solvatochromic effect was studied to observe the solvent effects on non-irradiation colouration of the photochromic dyes. Furthermore, The molecular energy levels for optimized geometries of the synthesized bis-azospiropyrans and their probable photochemical products were obtained at the B3LYP/6-31G(d) level of theory.

  19. Preparation of a Bis-GMA-Free Dental Resin System with Synthesized Fluorinated Dimethacrylate Monomers

    PubMed Central

    Luo, Shuzhen; Zhu, Wenbin; Liu, Fang; He, Jingwei

    2016-01-01

    With the aim of reducing human exposure to Bisphenol A (BPA) derivatives in dentistry, a fluorinated dimethacrylate monomer was synthesized to replace 2,2-bis[4-(2-hydroxy-3-methacryloy-loxypropyl)-phenyl]propane (Bis-GMA) as the base monomer of dental resin. After mixing with reactive diluent triethyleneglycol dimethacrylate (TEGDMA), fluorinated dimethacrylate (FDMA)/TEGDMA was prepared and compared with Bis-GMA/TEGDMA in physicochemical properties, such as double bond conversion (DC), volumetric shrinkage (VS), water sorption (WS) and solubility (WSL), flexural strength (FS) and modulus (FM). The results showed that, when compared with Bis-GMA based resin, FDMA-based resin had several advantages, such as higher DC, lower VS, lower WS, and higher FS after water immersion. All of these revealed that FDMA had potential to be used as a substitute for Bis-GMA. Of course, many more studies, such as biocompatibility testing, should be undertaken to prove whether FDMA could be applied in clinic. PMID:27916947

  20. New bis-N9-(methylphenylmethyl)purine derivatives: synthesis and antitumor activity.

    PubMed

    Kode, Nageswara; Chen, Liying; Murthy, Devangachinta; Adewumi, Dare; Phadtare, Shashikant

    2007-03-01

    A series of ortho-, meta- and para-bis-N9-(methylphenylmethyl)purine derivatives 4-15 were obtained by two-step synthesis from various substituted chloropurines with alpha,alpha'-dichloroxylenes. These bis-N9-(methylphenylmethyl)purines 4-15 were evaluated for the primary cytotoxic activity against a panel of NCI-H460 (lung), MCF-7 (breast) and SF-268 (CNS) cancer cell lines. The 'active' compounds which reduced growth of cancer cells to ca. 32% or less, have been evaluated in a full panel of 60 human cancer cell lines over a 5-log dose range at the National Cancer Institute, Bethesda, MD. In this series, the most activity is correlated to the compounds derived from the 2,6-dichloropurines such as bis-9-[o-(methylphenylmethyl)]2,6-dichloropurine (5), bis-9-[m-(methylphenylmethyl)]2,6-dichloropurine (8), and bis-9-[p-(methylphenylmethyl)]2,6-dichloropurine (11). In particular compound 8 exhibited high sensitivity in leukemia cell lines and compounds 5, 8 and 11 exhibited consistent high sensitivity in many breast cancer cell lines. Compound 11 was the most potent in this series and exhibited GI(50)<0.01 microM sensitivity against non-small lung cancer EKVX, colon cancer HT-29, melanoma SK-MEL-28, renal cancer RXF 393, prostate cancer DU-145 and several breast cancer HS 578T and BT-549 cell lines.

  1. Single-molecule kinetics and footprinting of DNA bis-intercalation: the paradigmatic case of Thiocoraline

    PubMed Central

    Camunas-Soler, Joan; Manosas, Maria; Frutos, Silvia; Tulla-Puche, Judit; Albericio, Fernando; Ritort, Felix

    2015-01-01

    DNA bis-intercalators are widely used in molecular biology with applications ranging from DNA imaging to anticancer pharmacology. Two fundamental aspects of these ligands are the lifetime of the bis-intercalated complexes and their sequence selectivity. Here, we perform single-molecule optical tweezers experiments with the peptide Thiocoraline showing, for the first time, that bis-intercalation is driven by a very slow off-rate that steeply decreases with applied force. This feature reveals the existence of a long-lived (minutes) mono-intercalated intermediate that contributes to the extremely long lifetime of the complex (hours). We further exploit this particularly slow kinetics to determine the thermodynamics of binding and persistence length of bis-intercalated DNA for a given fraction of bound ligand, a measurement inaccessible in previous studies of faster intercalating agents. We also develop a novel single-molecule footprinting technique based on DNA unzipping and determine the preferred binding sites of Thiocoraline with one base-pair resolution. This fast and radiolabelling-free footprinting technique provides direct access to the binding sites of small ligands to nucleic acids without the need of cleavage agents. Overall, our results provide new insights into the binding pathway of bis-intercalators and the reported selectivity might be of relevance for this and other anticancer drugs interfering with DNA replication and transcription in carcinogenic cell lines. PMID:25690887

  2. A RuBisCO-mediated carbon metabolic pathway in methanogenic archaea

    PubMed Central

    Kono, Takunari; Mehrotra, Sandhya; Endo, Chikako; Kizu, Natsuko; Matusda, Mami; Kimura, Hiroyuki; Mizohata, Eiichi; Inoue, Tsuyoshi; Hasunuma, Tomohisa; Yokota, Akiho; Matsumura, Hiroyoshi; Ashida, Hiroki

    2017-01-01

    Two enzymes are considered to be unique to the photosynthetic Calvin–Benson cycle: ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO), responsible for CO2 fixation, and phosphoribulokinase (PRK). Some archaea possess bona fide RuBisCOs, despite not being photosynthetic organisms, but are thought to lack PRK. Here we demonstrate the existence in methanogenic archaea of a carbon metabolic pathway involving RuBisCO and PRK, which we term ‘reductive hexulose-phosphate' (RHP) pathway. These archaea possess both RuBisCO and a catalytically active PRK whose crystal structure resembles that of photosynthetic bacterial PRK. Capillary electrophoresis-mass spectrometric analysis of metabolites reveals that the RHP pathway, which differs from the Calvin–Benson cycle only in a few steps, is active in vivo. Our work highlights evolutionary and functional links between RuBisCO-mediated carbon metabolic pathways in methanogenic archaea and photosynthetic organisms. Whether the RHP pathway allows for autotrophy (that is, growth exclusively with CO2 as carbon source) remains unknown. PMID:28082747

  3. Ultrafast spectroscopy and structural characterization of a photochromic isomerizing ruthenium bis-sulfoxide complex.

    PubMed

    King, Albert W; Malizia, Jason P; Engle, James T; Ziegler, Christopher J; Rack, Jeffrey J

    2014-12-21

    Irradiation of [Ru(bpy)2(bpSOp)](PF6)2 (where bpy is 2,2'-bipyridine and bpSOp is 1,3-bis(phenylsulfinyl)propane) results in the formation of two new isomers, namely the S,O- and O,O-bonded species. The crystal structure of the bis-thioether and bis-sulfoxide complexes are reported. NMR spectroscopy of the bis-thioether complex in solution is consistent with the molecular structure determined by diffraction methods. Further, NMR spectroscopy of the bis-sulfoxide complex reveals two conformers in solution, one that is consistent with the solid state structure and a second conformer showing distortion in the aliphatic portion of the chelate ring. Time-resolved visible absorption spectroscopy reveals isomerization time constants of 91 ps in dichloroethane (DCE) and 229 ps in propylene carbonate (PC). Aggregate isomerization quantum yields of 0.57 and 0.42 have been determined in DCE and in PC, respectively. The kinetics of the thermal reversion from the O,O- to S,O-bonded isomer are strongly solvent dependent, occurring with rates of 2.41 × 10(-3) and 4.39 × 10(-5) s(-1) in DCE, and 4.68 × 10(-4) and 9.79 × 10(-6) s(-1) in PC. The two kinetic components are assigned to the two isomers identified in solution.

  4. Preparation of a Bis-GMA-Free Dental Resin System with Synthesized Fluorinated Dimethacrylate Monomers.

    PubMed

    Luo, Shuzhen; Zhu, Wenbin; Liu, Fang; He, Jingwei

    2016-12-01

    With the aim of reducing human exposure to Bisphenol A (BPA) derivatives in dentistry, a fluorinated dimethacrylate monomer was synthesized to replace 2,2-bis[4-(2-hydroxy-3-methacryloy-loxypropyl)-phenyl]propane (Bis-GMA) as the base monomer of dental resin. After mixing with reactive diluent triethyleneglycol dimethacrylate (TEGDMA), fluorinated dimethacrylate (FDMA)/TEGDMA was prepared and compared with Bis-GMA/TEGDMA in physicochemical properties, such as double bond conversion (DC), volumetric shrinkage (VS), water sorption (WS) and solubility (WSL), flexural strength (FS) and modulus (FM). The results showed that, when compared with Bis-GMA based resin, FDMA-based resin had several advantages, such as higher DC, lower VS, lower WS, and higher FS after water immersion. All of these revealed that FDMA had potential to be used as a substitute for Bis-GMA. Of course, many more studies, such as biocompatibility testing, should be undertaken to prove whether FDMA could be applied in clinic.

  5. Poly[bis­(acetonitrile-κN)bis­[μ3-bis(tri­fluoro­methane­sulfonyl)­imido-κ4 O,O′:O′′:O′′′]dilithium

    PubMed Central

    Seo, Daniel M.; Boyle, Paul D.; Henderson, Wesley A.

    2011-01-01

    In the title compound, [Li2(CF3SO2NSO2CF3)2(CH3CN)2]n, two Li+ cations reside on crystallographic inversion centers, each coordinated by six O atoms from bis(trifluoromethanesulfonyl)imide (TFSI−) anions. The third Li+ cation on a general position is four-coordinated by two anion O atoms and two N atoms from acetonitrile mol­ecules in a tetra­hedral geometry. PMID:21754274

  6. 15 CFR Supplement No. 1 to Part 748 - BIS-748P, BIS-748P-A; Item Appendix, and BIS-748P-B; End-User Appendix; Multipurpose Application...

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... BIS-748P-A for additional items. (a) ECCN. Enter the Export Control Classification Number (ECCN) that... reexported, in terms of the “Unit” identified for the ECCN entered in Block 22(a). If the “Unit” for an item... within each ECCN will list a specific “Unit” for those items controlled by the entry. The “Unit” must...

  7. 15 CFR Supplement No. 1 to Part 748 - BIS-748P, BIS-748P-A; Item Appendix, and BIS-748P-B; End-User Appendix; Multipurpose Application...

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... BIS-748P-A for additional items. (a) ECCN. Enter the Export Control Classification Number (ECCN) that... reexported, in terms of the “Unit” identified for the ECCN entered in Block 22(a). If the “Unit” for an item... within each ECCN will list a specific “Unit” for those items controlled by the entry. The “Unit” must...

  8. 15 CFR Supplement No. 1 to Part 748 - BIS-748P, BIS-748P-A; Item Appendix, and BIS-748P-B; End-User Appendix; Multipurpose Application...

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... BIS-748P-A for additional items. (a) ECCN. Enter the Export Control Classification Number (ECCN) that... reexported, in terms of the “Unit” identified for the ECCN entered in Block 22(a). If the “Unit” for an item... within each ECCN will list a specific “Unit” for those items controlled by the entry. The “Unit” must...

  9. Synthesis and complexation properties of DTPA-N,N''-bis[bis(n-butyl)]-N'-methyl-tris(amide). Kinetic stability and water exchange of its Gd3+ complex.

    PubMed

    Jaszberényi, Z; Tóth, E; Kálai, T; Király, R; Burai, L; Brücher, E; Merbach, A E; Hideg, K

    2005-02-21

    A novel DTPA-tris(amide) derivative ligand, DTPA-N,N''-bis[bis(n-butyl)]-N'-methyl-tris(amide)(H2L3) was synthesized. With Gd3+, it forms a positively charged [Gd(L3)]+ complex, whereas with Cu2+ and Zn2+ [ML3], [MHL3]+ and [M2L3]2+ species are formed. The protonation constants of H2L3 and the stability constants of the complexes were determined by pH potentiometry. The stability constants are lower than those for DTPA-N,N''-bis[bis(n-butyl)amide)](H3L2), due to the lower negative charge and reduced basicity of the amine nitrogens in (L3)2-. The kinetic stability of [Gd(L3)]+ was characterised by the rates of metal exchange reactions with Eu3+, Cu2+ and Zn2+. The exchange reactions, which occur via proton and metal ion assisted dissociation of [Gd(L3)]+, are significantly slower than for [Gd(DTPA)]2-, since the amide groups cannot be protonated and interact only weakly with the attacking metal ions. The relaxivities of [Gd(L2)] and [Gd(L3)]+ are constant between 10-20 degrees C, indicating a relatively slow water exchange. Above 25 degrees C, the relaxivities decrease, similarly to other Gd3+ DTPA-bis(amide) complexes. The pH dependence of the relaxivities for [Gd(L3)]+ shows a minimum at pH approximately 9, thus differs from the behaviour of Gd3+-DTPA-bis(amides) which have constant relaxivities at pH 3-8 and an increase below and above. The water exchange rates for [Gd(L2)(H2O)] and [Gd(L3)(H2O)]+, determined from a variable temperature (17)O NMR study, are lower than that for [Gd(DTPA)(H2O)]2-. This is a consequence of the lower negative charge and decreased steric crowding at the water binding site in amides as compared to carboxylate analogues. Substitution of the third acetate of DTPA5- with an amide, however, results in a less pronounced decrease in kex than substitution of the first two acetates. The activation volumes derived from a variable pressure (17)O NMR study prove a dissociative interchange and a limiting dissociative mechanism for [Gd(L2)(H2O

  10. Proton transfer bis-benzazole fluors and their use in scintillator detectors

    DOEpatents

    Kauffman, Joel M.

    1994-01-01

    A novel class of proton transfer, bis-benzazole, fluorescent compounds, i.e., fluors, is disclosed. The novel fluors include substituted or unsubstituted 1,4-bis(2-benzazolyl)-2-hydroxybenzenes and 1,4-bis(2-benzazolyl)-2-amidobenzenes wherein the benzazolyl group may be benzoxazolyl, benzimidazolyl, benzothiazolyl, and the like. The benzazolyl groups may be substituted with one or more alkyl groups to improve solubility in organic matrix materials such as solvents, monomers, resins, polymers, and the like. The novel fluors may be used in the manufacture of fluorescent coatings, objects, scintillators, light sources and the like. The novel fluors are particularly useful for radiation-hard, solid scintillators for the detection and measurement of high energy particles and radiation.

  11. Proton transfer bis-benzazole fluors and their use in scintillator detectors

    DOEpatents

    Kauffman, J.M.

    1994-03-29

    A novel class of proton transfer, bis-benzazole, fluorescent compounds, i.e., fluors, is disclosed. The novel fluors include substituted or unsubstituted 1,4-bis(2-benzazolyl)-2-hydroxybenzenes and 1,4-bis(2-benzazolyl)-2-amidobenzenes wherein the benzazolyl group may be benzoxazolyl, benzimidazolyl, benzothiazolyl, and the like. The benzazolyl groups may be substituted with one or more alkyl groups to improve solubility in organic matrix materials such as solvents, monomers, resins, polymers, and the like. The novel fluors may be used in the manufacture of fluorescent coatings, objects, scintillators, light sources and the like. The novel fluors are particularly useful for radiation-hard, solid scintillators for the detection and measurement of high energy particles and radiation.

  12. Isolation of bis(copper) key intermediates in Cu-catalyzed azide-alkyne "click reaction".

    PubMed

    Jin, Liqun; Tolentino, Daniel R; Melaimi, Mohand; Bertrand, Guy

    2015-06-01

    The copper-catalyzed 1,3-dipolar cycloaddition of an azide to a terminal alkyne (CuAAC) is one of the most popular chemical transformations, with applications ranging from material to life sciences. However, despite many mechanistic studies, direct observation of key components of the catalytic cycle is still missing. Initially, mononuclear species were thought to be the active catalysts, but later on, dinuclear complexes came to the front. We report the isolation of both a previously postulated π,σ-bis(copper) acetylide and a hitherto never-mentioned bis(metallated) triazole complex. We also demonstrate that although mono- and bis-copper complexes promote the CuAAC reaction, the dinuclear species are involved in the kinetically favored pathway.

  13. openBIS ELN-LIMS: an open-source database for academic laboratories

    PubMed Central

    Barillari, Caterina; Ottoz, Diana S. M.; Fuentes-Serna, Juan Mariano; Ramakrishnan, Chandrasekhar; Rinn, Bernd; Rudolf, Fabian

    2016-01-01

    Summary: The open-source platform openBIS (open Biology Information System) offers an Electronic Laboratory Notebook and a Laboratory Information Management System (ELN-LIMS) solution suitable for the academic life science laboratories. openBIS ELN-LIMS allows researchers to efficiently document their work, to describe materials and methods and to collect raw and analyzed data. The system comes with a user-friendly web interface where data can be added, edited, browsed and searched. Availability and implementation: The openBIS software, a user guide and a demo instance are available at https://openbis-eln-lims.ethz.ch. The demo instance contains some data from our laboratory as an example to demonstrate the possibilities of the ELN-LIMS (Ottoz et al., 2014). For rapid local testing, a VirtualBox image of the ELN-LIMS is also available. Contact: brinn@ethz.ch or fabian.rudolf@bsse.ethz.ch PMID:26508761

  14. Vaporization behavior of tetraoctylphosphonium bis(2-ethylhexyl)phosphate ionic liquid

    NASA Astrophysics Data System (ADS)

    McMurray, J. W.; Zhou, Y.; Luo, H. M.; Qu, J.

    2017-01-01

    The equilibrium vapor pressures, pe, of the ionic liquid tetraoctylphosphonium bis(2-ethylhexyl)phosphate ([P8888][DEHP]) over the temperature range 409-495 K were determined for the first time using mass loss Knudsen effusion. The pe versus temperature relationship compares well to 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide ([C8mim][NTf2]) but is lower than that of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) when measured using the same technique. The discrepancies between the pe determined in this work for [C8mim][NTf2] and [C2mim][NTf2] with previous studies is discussed. The enthalpy and entropy of vaporization for all three fluids are estimated from the Clasius-Clapeyron relation.

  15. Influence of body position, food and beverage consumption on BIS measurements

    NASA Astrophysics Data System (ADS)

    Medrano, G.; Eitner, F.; Ismail, A. H.; Pikkemaat, R.; Cordes, A.; Floege, J.; Leonhardt, S.

    2010-04-01

    Continuous monitoring of fluid changes using bioimpedance spectroscopy (BIS) during hemodialysis could help to predict hypotensive complications and extend the patient's life. Food and beverage consumption during the treatment may influence the measurements and the calculated fluid removal. In the present article the change observed in whole body and segmental (knee-to-knee, abdomen) BIS measurements following a sequence similar to the one of dialysis treatment (lying down, sitting and eating, lying down) on healthy subjects is presented. The measurements have been performed using a commercial bioimpedance device with a frequency range of 5 kHz to 1 MHz. Knee-to-knee measurements seem to be less sensitive to these influences, compared to the standard whole body and the alternative abdomen BIS measurements. The results indicate that the individual influence of both body posture and food and beverage consumption may be superposed when combined.

  16. Synthesis of 1,3-bis(tetracyano-2-azulenyl-3-butadienyl)azulenes by the [2+2] cycloaddition-retroelectrocyclization of 1,3-bis(azulenylethynyl)azulenes with tetracyanoethylene.

    PubMed

    Shoji, Taku; Maruyama, Mitsuhisa; Maruyama, Akifumi; Ito, Shunji; Okujima, Tetsuo; Toyota, Kozo

    2014-09-08

    1,3-Bis(azulenylethynyl)azulene derivatives 9-14 have been prepared by palladium-catalyzed alkynylation of 1-ethynylazulene 8 with 1,3-diiodoazulene 1 or 1,3-diethynylazulene 2 with the corresponding haloazulenes 3-7 under Sonogashira-Hagihara conditions. Bis(alkynes) 9-14 reacted with tetracyanoethylene (TCNE) in a formal [2+2] cycloaddition-retroelectrocyclization reaction to afford the corresponding new bis(tetracyanobutadiene)s (bis(TCBDs)) 15-20 in excellent yields. The redox behavior of bis(TCBD)s 15-20 was examined by using CV and differential pulse voltammetry (DPV), which revealed their reversible multistage reduction properties under the electrochemical conditions. Moreover, a significant color change of alkynes 9-14 and TCBDs 15-20 was observed by visible spectroscopy under the electrochemical reduction conditions.

  17. Neurotoxicology of bis(n)-tacrines on Blattella germanica and Drosophila melanogaster acetylcholinesterase.

    PubMed

    Mutunga, James M; Boina, Dhana Raj; Anderson, Troy D; Bloomquist, Jeffrey R; Carlier, Paul R; Wong, Dawn M; Lam, Polo C-H; Totrov, Maxim M

    2013-08-01

    A series of bis(n)-tacrines were used as pharmacological probes of the acetylcholinesterase (AChE) catalytic and peripheral sites of Blattella germanica and Drosophila melanogaster, which express AChE-1 and AChE-2 isoforms, respectively. In general, the potency of bis(n)-tacrines was greater in D. melanogaster AChE (DmAChE) than in B. germanica AChE (BgAChE). The change in potency with tether length was high in DmAChE and low in BgAChE, associated with 90-fold and 5.2-fold maximal potency gain, respectively, compared to the tacrine monomer. The optimal tether length for Blattella was 8 carbons and for Drosophila was 10 carbons. The two species differed by only about twofold in their sensitivity to tacrine monomer, indicating that differential potency occurred among dimeric bis(n)-tacrines due to structural differences in the peripheral site. Multiple sequence alignment and in silico homology modeling suggest that aromatic residues of DmAChE confer higher affinity binding, and the lack of same at the BgAChE peripheral site may account, at least in part, to the greater overall sensitivity of DmAChE to bis(n)-tacrines, as reflected by in vitro assay data. Topical and injection assays in cockroaches found minimal toxicity of bis(n)-tacrines. Electrophysiological studies on D. melanogaster central nervous system showed that dimeric tacrines do not readily cross the blood brain barrier, explaining the observed nonlethality to insects. Although the bis(n)-tacrines were not good insecticide candidates, the information obtained in this study should aid in the design of selective bivalent ligands targeting insect, pests, and disease vectors.

  18. 40 CFR 721.10345 - 1,2-Benzenedicarboxylic acid, 1,2-bis(methylcyclohexyl) ester.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...(methylcyclohexyl) ester. 721.10345 Section 721.10345 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10345 1,2-Benzenedicarboxylic acid, 1,2-bis(methylcyclohexyl) ester. (a... 1,2-benzenedicarboxylic acid, 1,2-bis(methylcyclohexyl) ester (PMN P-05-110; CAS No. 27987-25-3)...

  19. 40 CFR 721.10345 - 1,2-Benzenedicarboxylic acid, 1,2-bis(methylcyclohexyl) ester.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...(methylcyclohexyl) ester. 721.10345 Section 721.10345 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10345 1,2-Benzenedicarboxylic acid, 1,2-bis(methylcyclohexyl) ester. (a... 1,2-benzenedicarboxylic acid, 1,2-bis(methylcyclohexyl) ester (PMN P-05-110; CAS No. 27987-25-3)...

  20. 40 CFR 721.10345 - 1,2-Benzenedicarboxylic acid, 1,2-bis(methylcyclohexyl) ester.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...(methylcyclohexyl) ester. 721.10345 Section 721.10345 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10345 1,2-Benzenedicarboxylic acid, 1,2-bis(methylcyclohexyl) ester. (a... 1,2-benzenedicarboxylic acid, 1,2-bis(methylcyclohexyl) ester (PMN P-05-110; CAS No. 27987-25-3)...

  1. New Tricks for an Old Measure: The Development of the Barratt Impulsiveness Scale-Brief (BIS-Brief)

    ERIC Educational Resources Information Center

    Steinberg, Lynne; Sharp, Carla; Stanford, Matthew S.; Tharp, Andra Teten

    2013-01-01

    The Barratt Impulsivity Scale (BIS), a 30-item self-report measure, is one of the most commonly used scales for the assessment of the personality construct of impulsiveness. It has recently marked 50 years of use in research and clinical settings. The current BIS-11 is held to measure 3 theoretical subtraits, namely, attentional, motor, and…

  2. 40 CFR 721.10334 - Ethanol, 2,2′-[(3-[(2-ethylhexyl)oxy]pentyl]imino]bis-].

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Ethanol, 2,2â²- pentyl]imino]bis... Specific Chemical Substances § 721.10334 Ethanol, 2,2′- pentyl]imino]bis-]. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-...

  3. 40 CFR 721.10334 - Ethanol, 2,2′-[(3-[(2-ethylhexyl)oxy]pentyl]imino]bis-].

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Ethanol, 2,2â²- pentyl]imino]bis... Specific Chemical Substances § 721.10334 Ethanol, 2,2′- pentyl]imino]bis-]. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-...

  4. 40 CFR 721.10334 - Ethanol, 2,2′-[(3-[(2-ethylhexyl)oxy]pentyl]imino]bis-].

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Ethanol, 2,2â²- pentyl]imino]bis... Specific Chemical Substances § 721.10334 Ethanol, 2,2′- pentyl]imino]bis-]. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanol, 2,2′-...

  5. 15 CFR Supplement No. 3 to Part 732 - BIS's “Know Your Customer” Guidance and Red Flags

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... ADMINISTRATION REGULATIONS STEPS FOR USING THE EAR Pt. 732, Supp. 3 Supplement No. 3 to Part 732—BIS's “Know Your Customer” Guidance and Red Flags “Know Your Customer” Guidance Various requirements of the EAR are... EAR has occurred or is about to occur. (a) BIS provides the following guidance on how individuals...

  6. 15 CFR Supplement No. 3 to Part 732 - BIS's “Know Your Customer” Guidance and Red Flags

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... ADMINISTRATION REGULATIONS STEPS FOR USING THE EAR Pt. 732, Supp. 3 Supplement No. 3 to Part 732—BIS's “Know Your Customer” Guidance and Red Flags “Know Your Customer” Guidance Various requirements of the EAR are... EAR has occurred or is about to occur. (a) BIS provides the following guidance on how individuals...

  7. 15 CFR Supplement No. 3 to Part 732 - BIS's “Know Your Customer” Guidance and Red Flags

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... ADMINISTRATION REGULATIONS STEPS FOR USING THE EAR Pt. 732, Supp. 3 Supplement No. 3 to Part 732—BIS's “Know Your Customer” Guidance and Red Flags “Know Your Customer” Guidance Various requirements of the EAR are... EAR has occurred or is about to occur. (a) BIS provides the following guidance on how individuals...

  8. 15 CFR Supplement No. 3 to Part 732 - BIS's “Know Your Customer” Guidance and Red Flags

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... ADMINISTRATION REGULATIONS STEPS FOR USING THE EAR Pt. 732, Supp. 3 Supplement No. 3 to Part 732—BIS's “Know Your Customer” Guidance and Red Flags “Know Your Customer” Guidance Various requirements of the EAR are... EAR has occurred or is about to occur. (a) BIS provides the following guidance on how individuals...

  9. Highly heteroselective ring-opening polymerization of racemic lactide initiated by divalent ytterbium complexes bearing amino bis(phenolate) ligands.

    PubMed

    Yang, Sheng; Du, Zhu; Zhang, Yong; Shen, Qi

    2012-10-09

    Polymerization of racemic lactide initiated by divalent ytterbium complexes supported by either dimethylamino-amino bis(phenolate) or methoxy-amino bis(phenolate) ligands proceeds rapidly at room temperature in a living fashion to give heterotactic polylactide with the racemic enchainment of monomer units P(r) ranging from 0.97-0.99.

  10. O2 reduction by a functional heme/nonheme bis-iron NOR model complex

    PubMed Central

    Collman, James P.; Dey, Abhishek; Yang, Ying; Ghosh, Somdatta; Decréau, Richard A.

    2009-01-01

    O2 reactivity of a functional NOR model is investigated by using electrochemistry and spectroscopy. The electrochemical measurements using interdigitated electrodes show very high selectivity for 4e O2 reduction with minimal production of partially reduced oxygen species (PROS) under both fast and slow electron flux. Intermediates trapped at cryogenic temperatures and characterized by using resonance Raman spectroscopy under single-turnover conditions indicate that an initial bridging peroxide intermediate undergoes homolytic OO bond cleavage generating a trans heme/nonheme bis-ferryl intermediate. This bis ferryl species can oxygenate 2 equivalents of a reactive substrate. PMID:19541624

  11. A Novel Bis-Thiourea Organocatalyst for the Asymmetric Aza-Henry Reaction

    PubMed Central

    Rampalakos, Constantinos; Wulff, William D.

    2013-01-01

    A novel bis-thiourea BINAM-based catalyst for the asymmetric aza-Henry reaction has been developed. This catalyst promotes the reaction of N-Boc imines with nitroalkanes to afford β-nitroamines with good yields and high enantioselectivities. This catalyst has the advantage that it can be prepared in a single step from commercially available materials. A model is proposed for the catalyst action where the both components of the reaction are activated simultaneously by hydrogen bonding. Regardless of the mechanism, the success of the present catalyst demonstrates the potential of bis-thioureas as an interesting class of relatively unexplored catalysts. PMID:23795151

  12. Endovascular coil detachment causing EMG artefact in BIS: a mechanistic exploration.

    PubMed

    Chakrabarti, Dhritiman; Ramesh, Venkatapura J; Pendharkar, Hima

    2016-04-01

    Deployment of endovascular coils used in interventional neuroradiology commonly involves electrolytic detachment of the coil from the pusher catheter. This report describes a case of artefactual increase in electromyography (EMG) values of bispectral index (BIS) monitor during coil detachment. An explanation of this event is provided connecting mechanism of coil detachment and derivation of EMG values in a BIS monitor. While rising EMG values are thought to arise from frontalis contraction, they may as well be an unrecognized electrical artefact, especially in context of undistorted electroencephalography waveform.

  13. Lithium bromide-induced structural changes in a nickel bis-alkoxide complex.

    PubMed

    Ichiokai, Hiromi; Vicic, David A

    2013-01-01

    The bis-alkoxide [(DEAMP)2Ni] (1, DEAMP = 1-(diethylamino)-2-methylpropan-2-olate) was found to react with trace amounts of lithium bromide to afford the bis-LiBr adduct 2, in which the oxygens of the DEAMP ligand coordinate to lithium to form a chiral-at-metal complex. This new complex is five-coordinate at nickel, and contains nickel and oxygen atoms which are all chiral. One diastereomer precipitates from pentane solution. The two lithium ions rigidify the new structure in the solid state by coordinating to the oxygen and bromide atoms.

  14. Impact of age on both BIS values and EEG bispectrum during anaesthesia with sevoflurane in children

    PubMed Central

    Wodey, Eric; Tirel, Olivier; Bansard, Jean-Yves; Terrier, Anne; Chanavaz, Charles; Harris, Rupert; Ecoffey, Claude; Senhadji, Lotfi

    2005-01-01

    The aim of this study was to evaluate the potential relationship between age, BIS (Aspect™) and the EEG bispectrum during anesthesia with sevoflurane. BIS and raw EEG sampled at 400 Hz were recorded at a steady state of 1 MAC sevoflurane in 100 children, and during a decrease from 2 MAC to 0.5 MAC in a sub-group of 29 children. The bispectrum of the EEG was estimated on successive epochs of 20 seconds using MATLAB© software, independently of the Aspect™ device. For analysis, the bispectrum was divided into 36 frequencies of coupling (Pi) - the MatBis. A multiple correspondence analysis (MCA) was used to establish an underlying structure of the pattern of each individual’s MatBis at the steady state of 1 MAC. Clustering of children into homogeneous groups was conducted by a hierarchical ascending classification (HAC). The level of statistical significance was set at 0.05. At the steady state of 1 MAC sevoflurane, the BIS values for all 100 children ranged from 20 to 74 (median 40). Projection of both age and BIS value recorded at 1 MAC (T10) onto the structured model of the MCA showed them to be distributed along axis F1 of this model. In contrast, projection of children’s position during the decrease in sevoflurane concentration was linked to axis F2. At 1 MAC sevoflurane, six homogeneous groups of children were obtained through the HAC. Groups 5 (30 months; range 23–49) and 6 (18 months; range 6–180) were the younger children and group 1 (97 months; range 46–162) the older. Groups 5 and 6 had the highest median values of BIS (54; range 50–59)(55; range 26–74) and the group 1 the lowest values (29; range 22–37). The EEG bispectrum, as well as the BIS (Aspect XP™) measured at 1 MAC sevoflurane appeared to be strongly related to the age of children. PMID:15833781

  15. Selective DNA purine base photooxidation by bis-terdentate iridium(III) polypyridyl and cyclometalated complexes.

    PubMed

    Jacques, Alexandre; Kirsch-De Mesmaeker, Andrée; Elias, Benjamin

    2014-02-03

    Two bis-terdentate iridium(III) complexes with polypyridyl and cyclometalated ligands have been prepared and characterized. Their spectroscopic and electrochemical properties have been studied, and a photophysical scheme addressing their properties is proposed. Different types of excited states have been considered to account for the deactivation processes in each complex. Interestingly, in the presence of mono- or polynucleotides, a photoinduced electron-transfer process from a DNA purine base (i.e., guanine or adenine) to the excited complex is shown through luminescence quenching experiments. For the first time, this work reports evidence for selective DNA purine bases oxidation by excited iridium(III) bis-terdentate complexes.

  16. Regiochemically controlled synthesis of a β-4-β' [70]fullerene bis-adduct

    DOE PAGES

    Cerón, Maira R.; Castro, Edison; Neti, Venkata S. Pavan K.; ...

    2016-12-22

    A β-4-β' C70 bis-adduct regioisomer and an uncommon mono-adduct β-malonate C70 derivative were synthesized by using a Diels–Alder cycloaddition followed by an addition–elimination of bromo-ethylmalonate and a retro-Diels–Alder cycloaddition reaction. Here, we also report the regioselective synthesis and spectroscopic characterization of Cs-symmetric tris- and C2v-symmetric tetra-adducts of C70, which are the precursors of the mono- and bis-adduct final products.

  17. Regiochemically controlled synthesis of a β-4-β' [70]fullerene bis-adduct

    SciTech Connect

    Cerón, Maira R.; Castro, Edison; Neti, Venkata S. Pavan K.; Dunk, Paul W.; Echegoyen, Luis A.

    2016-12-22

    A β-4-β' C70 bis-adduct regioisomer and an uncommon mono-adduct β-malonate C70 derivative were synthesized by using a Diels–Alder cycloaddition followed by an addition–elimination of bromo-ethylmalonate and a retro-Diels–Alder cycloaddition reaction. Here, we also report the regioselective synthesis and spectroscopic characterization of Cs-symmetric tris- and C2v-symmetric tetra-adducts of C70, which are the precursors of the mono- and bis-adduct final products.

  18. Parent and teacher ratings of temperamental disposition to social anxiety: the BIS 3-6.

    PubMed

    Ballespí, Sergi; Jané, M Claustre; Riba, M Dolors

    2012-01-01

    Behavioral inhibition (BI) discourages children from interacting, predisposing them to isolation, social anxiety, and depression. We have created the Behavioral Inhibition Scale for Children Aged 3 to 6 (BIS 3-6) to detect this trait early. Parents and teachers of 365 preschoolers completed different versions of the BIS 3-6 and provided measures of psychopathology. Both versions are structured into 1 factor that explains over 40% of total variability and displays excellent internal consistency (α = .95). The moderate correlations with measures of internalizing symptoms (r = .50) and nonexistent correlations with externalizing measures suggest adequate convergent and discriminant validity. A new scoring system is proposed.

  19. Selective synthesis of mono- and bis-butenolide α-aminomethyl adducts.

    PubMed

    Talbi, Arbia; Arfaoui, Aïcha; Bsaibess, Talia; Lotfi Efrit, Mohamed; Gaucher, Anne; Prim, Damien; M Rabet, Hédi

    2017-03-30

    The selective installation of α-methylamine residues at the butenolide core is described using α-bromomethylene-γ-butenolide and primary as well as secondary amines in methanol at 0 °C. The preparation of mono- and bis-butenolide α-adducts is described. Bis-γ-butenolide adducts as well as mono α-aminomethyl-γ-butenolides can be selectively obtained depending on the nature of the reacting primary amine. In contrast, the use of secondary amines allows two different pathways leading either to the expected amino derivatives or to the formation of a C-O bond.

  20. O2 reduction by a functional heme/nonheme bis-iron NOR model complex.

    PubMed

    Collman, James P; Dey, Abhishek; Yang, Ying; Ghosh, Somdatta; Decréau, Richard A

    2009-06-30

    O(2) reactivity of a functional NOR model is investigated by using electrochemistry and spectroscopy. The electrochemical measurements using interdigitated electrodes show very high selectivity for 4e O(2) reduction with minimal production of partially reduced oxygen species (PROS) under both fast and slow electron flux. Intermediates trapped at cryogenic temperatures and characterized by using resonance Raman spectroscopy under single-turnover conditions indicate that an initial bridging peroxide intermediate undergoes homolytic O--O bond cleavage generating a trans heme/nonheme bis-ferryl intermediate. This bis ferryl species can oxygenate 2 equivalents of a reactive substrate.

  1. Synthesis and characterisation of bis-cyclen based dinuclear lanthanide complexes.

    PubMed

    Gunnlaugsson, Thorfinnur; Harte, Andrew J

    2006-04-21

    The design and synthesis of several bis-macrocyclic cyclen (1,4,7,10-tetraazacyclododecane) ligands and their corresponding lanthanum or europium complexes is described; these dinuclear lanthanide systems were made by connecting two macrocyclic cyclen moieties through a rigid, covalent, p-xylylenediamide bridge or a flexible aliphatic hexane bridge. These ligands were subsequently functionalised with six acetamide pendant arms (CONR1R2: R1 = R2 = H or CH3, or R1 = H, R2 = CH3). The corresponding lanthanide bis-complexes were then formed by reaction with La(III) and Eu(III) triflates, yielding overall cationic (+VI charged) complexes.

  2. Chromatographic Separation Method for the Simulant Mixture of Triisopropyl Phosphite and Bis(2-Ethylhexyl) Hydrogen Phosphite

    DTIC Science & Technology

    1991-08-01

    8217 Retention Time 2 (min) Area3 1. 2-propanol 1.1 981078 2. TIP 3.44 15685456 3. DIP 5.68 7205570 4. TIPO 1.15 3584104 5. --- 14.63 720318 6. 17.63...4. DIP 6.42 2001 5. TIPO 9.87 5949 6. 12.21 507 7. BIS impurity 13.48 454 8. 14.55 1854 9. --- 19.2 1594 10. BIS 19.76 17757 IThe identification of

  3. Electrochemical synthesis and structural characterization of a novel mixed-valence copper(I)-copper(II) complex: {[bis(ethylenediamine)copper(II)] bis[diiodocuprate(I)]}.

    PubMed

    Fotouhi, Lida; Dehghanpour, Saeed; Heravi, Majid M; Ardakani, Mahboobeh Dashti

    2007-07-12

    A novel, mixed-valent copper(I)-copper(II) complex, {[bis(ethylene-diamine)copper(II)] bis[diiodocuprate(I)]} (1), has been prepared by electrochemical dissolution of a sacrificial copper anode in a solution of ethylenediamine (en), I2 and tetraethylammoniumperchlorate (TEAP) as supporting electrolyte in acetonitrile (AcN)and characterized by single-crystal X-ray structure determination. The crystal structure of the complex 1 shows that it consists of a CuI2 polymer formed from I- ligands bridging Cu(I) ions, with a nearly square planar geometry of bivalent Cu(II) atoms chelated by two ethylenediamine ligands. The results also show that direct electrosynthesis of the complex had high current efficiency, purity and electrolysis yield.

  4. Direct Electrodeposition of UO2 from Uranyl Bis(trifluoromethanesulfonyl)imide Dissolved in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Room Temperature Ionic Liquid System

    DOE PAGES

    Freiderich, John W.; Wanigasekara, Eranda P.; Sun, Xiao-Guang; ...

    2013-11-11

    Our study demonstrates a direct electrodeposition of UO2 at a Pt cathode from a solution of uranyl bis(trifluoromethanesulfonyl)imide [UO2(NTf2)2)] in a bulk room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM+NTf2–). Cyclic voltammetry (CV) studies revealed two reduction waves corresponding to the conversion of uranium(VI) to uranium(IV), and a mechanism for the overall electroreduction is proposed. A controlled-potential experiment was performed, holding the reduction potential at–1.0 V for 24 h to obtain a brown-black deposit of UO2 on the Pt cathode. The Faradaic efficiency of the reduction process was determined to be >80%. The UO2deposit was characterized by powder X-ray diffraction (XRD)more » and X-ray photoelectron spectroscopy (XPS).« less

  5. Investigation of Ternary Mixtures Containing 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)azanide, Ethylene Carbonate and Lithium Bis(trifluoromethanesulfonyl)azanide

    PubMed Central

    Hofmann, Andreas; Migeot, Matthias; Arens, Lukas; Hanemann, Thomas

    2016-01-01

    Temperature-dependent viscosity, conductivity and density data of ternary mixtures containing 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)azanide (EMIM-TFSA), ethylene carbonate (EC), and lithium bis(trifluoromethanesulfonyl)azanide (Li-TFSA) were determined at atmospheric pressure in the temperature range of 20 to 80 °C. Differential scanning calorimetry (DSC) measurements were performed to characterize phase conditions of the mixtures in a temperature range of −120 to +100 °C. The viscosity data were fitted according to the Vogel-Fulcher-Tammann-Hesse (VFTH) equation and analyzed with the help of the fractional Walden rule. In this study, fundamental physicochemical data about the mixtures are provided and discussed as a basis for structure-property relationship calculations and for potential use of those mixtures as electrolytes for various applications. PMID:27153066

  6. Poly [1,1'-bis(ethynyl)-4,4'-biphenyl(bis-tributylphosphine)Pt(II)] solutions used as low dose ionizing radiation dosimeter

    SciTech Connect

    Bronze-Uhle, E. S.; Graeff, C. F. O.; Batagin-Neto, A.; Fernandes, D. M.; Fratoddi, I.; Russo, M. V.

    2013-06-17

    In this work, the effect of gamma radiation on the optical properties of polymetallayne poly[1,1'-bis(ethynyl)-4,4'-biphenyl(bis-tributylphosphine)Pt(II)] (Pt-DEBP) in chloroform solution is studied. The samples were irradiated at room temperature with doses from 0.01 Gy to 1 Gy using a {sup 60}Co gamma ray source. A new band at 420 nm is observed in the emission spectra, in superposition to the emission maximum at 398 nm, linearly dependent on dose. We propose to use the ratio of the emission amplitude bands as the dosimetric parameter. This method proved to be robust, accurate, and can be used as a dosimeter in medical applications.

  7. Structure-activity study for (bis)ureidopropyl- and (bis)thioureidopropyldiamine LSD1 inhibitors with 3-5-3 and 3-6-3 carbon backbone architectures.

    PubMed

    Nowotarski, Shannon L; Pachaiyappan, Boobalan; Holshouser, Steven L; Kutz, Craig J; Li, Youxuan; Huang, Yi; Sharma, Shiv K; Casero, Robert A; Woster, Patrick M

    2015-04-01

    Methylation at specific histone lysine residues is a critical post-translational modification that alters chromatin architecture, and dysregulated lysine methylation/demethylation is associated with the silencing of tumor suppressor genes. The enzyme lysine-specific demethylase 1 (LSD1) complexed to specific transcription factors catalyzes the oxidative demethylation of mono- and dimethyllysine 4 of histone H3 (H3K4me and H3K4me2, respectively). We have previously reported potent (bis)urea and (bis)thiourea LSD1 inhibitors that increase cellular levels of H3K4me and H3K4me2, promote the re-expression of silenced tumor suppressor genes and suppress tumor growth in vitro. Here we report the design additional (bis)urea and (bis)thiourea LSD1 inhibitors that feature 3-5-3 or 3-6-3 carbon backbone architectures. Three of these compounds displayed single-digit IC50 values in a recombinant LSD1 assay. In addition, compound 6d exhibited an IC50 of 4.2μM against the Calu-6 human lung adenocarcinoma line, and 4.8μM against the MCF7 breast tumor cell line, in an MTS cell viability assay. Following treatment with 6b-6d, Calu-6 cells exhibited a significant increase in the mRNA expression for the silenced tumor suppressor genes SFRP2, HCAD and p16, and modest increases in GATA4 message. The compounds described in this paper represent the most potent epigenetic modulators in this series, and have potential for use as antitumor agents.

  8. Structure-activity study for (bis)ureidopropyl- and (bis)thioureidopropyldiamine LSD1 inhibitors with 3-5-3 and 3-6-3 carbon backbone architectures

    PubMed Central

    Nowotarski, Shannon L.; Pachaiyappan, Boobalan; Holshouser, Steven L.; Kutz, Craig J.; Li, Youxuan; Huang, Yi; Sharma, Shiv K.; Casero, Robert A.; Woster, Patrick M.

    2015-01-01

    Methylation at specific histone lysine residues is a critical post-translational modification that alters chromatin architecture, and dysregulated lysine methylation/demethylation is associated with the silencing of tumor suppressor genes. The enzyme lysine-specific demethylase 1 (LSD1) complexed to specific transcription factors catalyzes the oxidative demethylation of mono- and dimethyllysine 4 of histone H3 (H3K4me and H3K4me2 respectively). We have previously reported potent (bis)urea and (bis)thiourea LSD1 inhibitors that increase cellular levels of H3K4me and H3K4me2, promote the re-expression of silenced tumor suppressor genes and suppress tumor growth in vitro. Here we report the design additional (bis)urea and (bis)thiourea LSD1 inhibitors that feature 3-5-3 or 3-6-3 carbon backbone architectures. Three of these compounds displayed single-digit IC50 values in a recombinant LSD1 assay. In addition, compound 6d exhibited an IC50 of 4.2 μM against the Calu-6 human lung adenocarcinoma line, and 4.8 μM against the MCF7 breast tumor cell line, in an MTS cell viability assay. Following treatment with 6b–6d, Calu-6 cells exhibited a significant increase in the mRNA expression for the silenced tumor suppressor genes SFRP2, HCAD and p16, and modest increases in GATA4 message. The compounds described in this paper represent the most potent epigenetic modulators in this series, and have potential for use as antitumor agents. PMID:25725609

  9. Fluorescent sensing and electrocatalytic properties of three Zn(II)/Co(II) coordination complexes containing two different dicarboxylates and two various bis(pyridyl)-bis(amide) ligands

    NASA Astrophysics Data System (ADS)

    Lin, Hongyan; Rong, Xing; Liu, Guocheng; Wang, Xiang; Wang, Xiuli; Duan, Surui

    2016-09-01

    Three new transition metal(II) coordination complexes constructed from two different dicarboxylates (1,3-H2BDC = 1,3-benzenedicarboxylic acid, 1,4-H2NDC = 1,4-naphthalenedicarboxylic acid) and two bis(pyridyl)-bis(amide) ligands (3-bpcd = N,N‧-bis(3-pyridyl)cyclohexane-1,4-dicarboxamide, 3-bpod = N,N‧-bis(3-pyridyl)octandiamide), [Zn(1,3-BDC)(3-bpcd)0.5(H2O)]·H2O (1), [Zn(1,3-BDC)(3-bpod)0.5(H2O)] (2) and [Co(1,4-NDC)(3-bpod)1.5(H2O)] (3) have been synthesized in the hydrothermal environments and structurally characterized by IR, TG and single crystal X-ray diffraction. Complexes 1 and 2 possess the similar 1D ladder-like chain based on [Zn(1,3-BDC)]n zigzag chain and the bidentate ligands 3-bpcd/or 3-bpod. Complex 3 shows a 2D layered structure with a 5-connected {410} topology, which consists of 1D linear [Co(1,4-NDC)]n chain and [Co(3-bpod)1.5]n chain with alternating arrangement of 3-bpod ligands and Co2(3-bpod)2 dinuclear loops. The adjacent 1D chains for 1-2 or the 2D layers for 3 are further extended into 2D or 3D supramolecular frameworks through the hydrogen bonding interactions. Additionally, the solid state fluorescent properties for the title complexes 1-3, the fluorescent sensing behaviors of complexes 1-2 and the electrochemical behaviour of complex 3 have been investigated.

  10. Convenient synthesis of bis(benzo)-fused BEDT-TTF and higher homologues: new electron donor molecules for organic charge transfer salts and `molecular rulers`

    SciTech Connect

    Parakka, J.P.; Kini, A.M.; Williams, J.M.

    1996-10-01

    A convenient synthesis of bis(benzo)- and bis(naphtho)-fused bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) derivatives, employing the [4+2] cycloaddition reaction of oligo(1,3-dithiole-2,4, 5-trithione) with appropriate alkenes as a key step, is presented.

  11. 40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates (salts). 721.3152 Section 721... Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates... ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

  12. 40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates (salts). 721.3152 Section 721... Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates... ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

  13. 40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates (salts). 721.3152 Section 721... Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates... ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

  14. 40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates (salts). 721.3152 Section 721... Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates... ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

  15. 40 CFR 721.10580 - Poly[oxy (methyl - 1,2 - ethanediyl)], alpha, alpha′ - [1,4 - cyclohexanediylbis(methylene)] bis...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Poly , alpha, alphaâ² - bis [omega... Significant New Uses for Specific Chemical Substances § 721.10580 Poly , alpha, alpha′ - bis [omega - (2... substance identified as poly , alpha, alpha′ - bis [omega - (2 - aminomethylethoxy) - (PMN P-10-452; CAS...

  16. 40 CFR 721.10580 - Poly[oxy(methyl-1,2- ethanediyl)], alpha, alpha′-[1,4- cyclohexanediylbis(methylene)] bis [omega...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Poly , alpha, alphaâ²- bis [omega-(2... Specific Chemical Substances § 721.10580 Poly , alpha, alpha′- bis [omega-(2-aminomethylethoxy)-. (a... poly , alpha, alpha′- bis [omega-(2- aminomethylethoxy)- (PMN P-10-452; CAS No. 1220986-58-2)...

  17. Effective remediation of phenol,2,4-bis(1,1-dimethylethyl) and bis(2-ethylhexyl) phthalate in farm effluent using Guar gum--A plant based biopolymer.

    PubMed

    Kee, Yang Ling; Mukherjee, Sumona; Pariatamby, Agamuthu

    2015-10-01

    This study was carried out to evaluate the efficiency of Guar gum in removing Persistent Organic Pollutants (POPs), viz. phenol,2,4-bis(1,1-dimethylethyl) and bis(2-ethylhexyl) phthalate (DEHP), from farm effluent. The removal efficiency was compared with alum. The results indicated that 4.0 mg L(-1) of Guar gum at pH 7 could remove 99.70% and 99.99% of phenol,2,4-bis(1,1-dimethylethyl) and DEHP, respectively. Box Behnken design was used for optimization of the operating parameters for optimal POPs removal. Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) spectroscopy studies were conducted on the flocs. SEM micrographs showed numerous void spaces in the flocs produced by Guar gum as opposed to those produced by alum. This indicated why Guar gum was more effective in capturing and removal of suspended particles and POPs as compared to alum. FTIR spectra indicated a shift in the bonding of functional groups in the flocs produced by Guar gum as compared to raw Guar gum powder signifying chemical attachment of the organics present in the effluent to the coagulant resulting in their removal. Guar gum is highly recommended as a substitute to chemical coagulant in treating POPs due to its non-toxic and biodegradable characteristics.

  18. A New Epoxy Bis-Phosphonate Crosslinker for Durable Fire Retardancy on Cotton

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new epoxy bis-phosphonate crosslinker for cotton [2-(dimethoxy-phosphorylmethyl)-oxiranylmethyl]-phosphonic acid dimethyl ester was prepared in two steps from 3-chloro-2-chloromethylpropene in 55% yield. The new monomer was characterized by proton and carbon NMR and GC-mass spectrometry. This cro...

  19. A Convenient Synthetic Protocol to 1,2-Bis(dialkylphosphino)ethanes

    PubMed Central

    Doyle, Laurence R; Heath, Alex; Low, Choon Heng; Ashley, Andrew E

    2014-01-01

    1,2-Bis(dialkylphosphino)ethanes are readily prepared from the parent phosphine oxides, via a novel sodium aluminium hydride/sodium hydride reduction protocol of intermediate chlorophosphonium chlorides. This approach is amenable to multi-gram syntheses, utilises readily available and inexpensive reagents, and benefits from a facile non-aqueous work-up in the final reductive step. PMID:26190960

  20. 40 CFR 721.1850 - Toluene sulfonamide bis-phe-nol A epoxy adduct.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... epoxy adduct. 721.1850 Section 721.1850 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.1850 Toluene sulfonamide bis-phe-nol A epoxy adduct. (a) Chemical... as toluene sulfonamide bisphenol A epoxy adduct (PMN P-90-113) is subject to reporting under...

  1. 40 CFR 721.1850 - Toluene sulfonamide bis-phe-nol A epoxy adduct.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... epoxy adduct. 721.1850 Section 721.1850 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.1850 Toluene sulfonamide bis-phe-nol A epoxy adduct. (a) Chemical... as toluene sulfonamide bisphenol A epoxy adduct (PMN P-90-113) is subject to reporting under...

  2. 40 CFR 721.1850 - Toluene sulfonamide bis-phe-nol A epoxy adduct.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... epoxy adduct. 721.1850 Section 721.1850 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.1850 Toluene sulfonamide bis-phe-nol A epoxy adduct. (a) Chemical... as toluene sulfonamide bisphenol A epoxy adduct (PMN P-90-113) is subject to reporting under...

  3. 40 CFR 721.1850 - Toluene sulfonamide bis-phe-nol A epoxy adduct.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... epoxy adduct. 721.1850 Section 721.1850 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.1850 Toluene sulfonamide bis-phe-nol A epoxy adduct. (a) Chemical... as toluene sulfonamide bisphenol A epoxy adduct (PMN P-90-113) is subject to reporting under...

  4. 40 CFR 721.1850 - Toluene sulfonamide bis-phe-nol A epoxy adduct.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... epoxy adduct. 721.1850 Section 721.1850 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.1850 Toluene sulfonamide bis-phe-nol A epoxy adduct. (a) Chemical... as toluene sulfonamide bisphenol A epoxy adduct (PMN P-90-113) is subject to reporting under...

  5. On the existence of 'bis (L-glutamine) potassium nitrate' crystal.

    PubMed

    Srinivasan, Bikshandarkoil R; Shyama, Soorambail K; Naik, Suvidha G; Jyai, Rita N

    2015-02-05

    The slow evaporation of an aqueous solution containing L-glutamine and potassium nitrate in 2:1 mol ratio results in the fractional crystallization of L-glutamine and not the formation of a so called bis (L-glutamine) potassium nitrate as reported recently by Hanumantharao and Kalainathan (2012).

  6. Synthesis and characterization of complexes of rare earth picrates and rac-bis(ethylsulfinyl)methane

    SciTech Connect

    Andrade Da Silva, M.A.; Zaim, M.H.; Isolani, P.C.

    1995-12-31

    The compound {beta}-dissulfoxide bis(ethylsufinyl)methane (besm) was prepared by oxidation of bis(ethylthio)methane with hydrogen peroxide in acetic acid, and obtained as a mixture of its meso and d,1 diastereomers. An analytical sample was obtained by recrystallization from chloroform-diethyl ether. The racemic-bis(ethylsulfinyl)methane was characterized and studied by CHS elemental analysis, high resolution mass spectrometry, infrared spectra, {sup 1}H and {sup 13}C NMR. A series of compounds with composition RE(pic){sub 3}2rac-besm [RE = La, Ce, Nd, Eu, Gd, Er, Tm, Yb, Lu and Y; pic = picrate and rac-besm = racemic-bis(ethylsulfinyl)methane] were synthesized and characterized by CHNS elemental analysis and rare earths complexometric titration with EDTA, conductance measurements, X-ray powder patterns, infrared spectra, visible absorption of the neodymium and emission spectra of the europium materials. The coordination polyhedron around the Eu{sup 3+} center is probably a dodecahedron with coordination number eight. 19 refs., 2 figs., 4 tabs.

  7. Hybrid Intelligent System to Perform Fault Detection on BIS Sensor During Surgeries

    PubMed Central

    Casteleiro-Roca, José-Luis; Calvo-Rolle, José Luis; Méndez Pérez, Juan Albino; Roqueñí Gutiérrez, Nieves; de Cos Juez, Francisco Javier

    2017-01-01

    This paper presents a new fault detection system in hypnotic sensors used for general anesthesia during surgery. Drug infusion during surgery is based on information received from patient monitoring devices; accordingly, faults in sensor devices can put patient safety at risk. Our research offers a solution to cope with these undesirable scenarios. We focus on the anesthesia process using intravenous propofol as the hypnotic drug and employing a Bispectral Index (BISTM) monitor to estimate the patient’s unconsciousness level. The method developed identifies BIS episodes affected by disturbances during surgery with null clinical value. Thus, the clinician—or the automatic controller—will not take those measures into account to calculate the drug dose. Our method compares the measured BIS signal with expected behavior predicted by the propofol dose provider and the electromyogram (EMG) signal. For the prediction of the BIS signal, a model based on a hybrid intelligent system architecture has been created. The model uses clustering combined with regression techniques. To validate its accuracy, a dataset taken during surgeries with general anesthesia was used. The proposed fault detection method for BIS sensor measures has also been verified using data from real cases. The obtained results prove the method’s effectiveness. PMID:28106793

  8. ALTERED TRANSCRIPTIONAL RESPONSES OF MOUSE EMBRYO CULTURES EXPOSED TO BISINDOLYLMALEIMIDE (BIS L)

    EPA Science Inventory

    Altered transcriptional responses in mouse embryos exposed to bisindolylmaleimide I (Bis I) in whole embryo culture

    Edward D. Karoly?*, Judith E. Schmid*, Maria R. Blanton*and E. Sidney Hunter III*
    ?Curriculum in Toxicology, University of North Carolina at Chapel Hill, ...

  9. N-doping of organic semiconductors by bis-metallosandwich compounds

    SciTech Connect

    Barlow, Stephen; Qi, Yabing; Kahn, Antoine; Marder, Seth; Kim, Sang Bok; Mohapatra, Swagat K.; Guo, Song

    2016-01-05

    The various inventions disclosed, described, and/or claimed herein relate to the field of methods for n-doping organic semiconductors with certain bis-metallosandwich compounds, the doped compositions produced, and the uses of the doped compositions in organic electronic devices. Metals can be manganese, rhenium, iron, ruthenium, osmium, rhodium, or iridium. Stable and efficient doping can be achieved.

  10. Highly selective bis(imino)pyridine iron-catalyzed alkene hydroboration.

    PubMed

    Obligacion, Jennifer V; Chirik, Paul J

    2013-06-07

    Bis(imino)pyridine iron dinitrogen complexes have been shown to promote the anti-Markovnikov catalytic hydroboration of terminal, internal, and geminal alkenes with high activity and selectivity. The isolated iron dinitrogen compounds offer distinct advantages in substrate scope and overall performance over known precious metal catalysts and previously reported in situ generated iron species.

  11. Bis-sulfonic acid ionic liquids for the conversion of fructose to 5-hydroxymethyl-2-furfural.

    PubMed

    Sim, Sang Eun; Kwon, Sunjeong; Koo, Sangho

    2012-10-31

    Homogenous bis-sulfonic acid ionic liquids (1 mol equiv.) in DMSO (10 mol equiv.) at 100 °C efficiently mediated the conversion of D-fructose into 5-hydroxymethyl-2-furfural in 75% isolated yield, which was roughly a 10% increment compared to the case of the mono-sulfonic acid ionic liquids.

  12. 40 CFR 721.10666 - Quaternary ammonium compounds, bis(fattyalkyl) dimethyl, salts with tannins (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10666 Quaternary ammonium compounds, bis(fattyalkyl) dimethyl, salts with tannins (generic). (a) Chemical substance and significant...

  13. 15 CFR 734.6 - Assistance available from BIS for determining licensing and other requirements.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... commodity, software, technology, or activity is subject to the EAR, or is subject to licensing or other requirements under the EAR, you may ask BIS for an advisory opinion, classification, or a determination whether a particular item or activity is subject to the EAR. In many instances, including those where...

  14. 15 CFR 712.8 - Declarations and reports returned without action by BIS.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 15 Commerce and Foreign Trade 2 2011-01-01 2011-01-01 false Declarations and reports returned without action by BIS. 712.8 Section 712.8 Commerce and Foreign Trade Regulations Relating to Commerce and Foreign Trade (Continued) BUREAU OF INDUSTRY AND SECURITY, DEPARTMENT OF COMMERCE CHEMICAL...

  15. 15 CFR Appendix I to Part 700 - Form BIS-999-Request for Special Priorities Assistance

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 15 Commerce and Foreign Trade 2 2010-01-01 2010-01-01 false Form BIS-999-Request for Special Priorities Assistance I Appendix I to Part 700 Commerce and Foreign Trade Regulations Relating to Commerce... SECURITY INDUSTRIAL BASE REGULATIONS DEFENSE PRIORITIES AND ALLOCATIONS SYSTEM Pt. 700, App. I Appendix...

  16. 15 CFR Appendix I to Part 700 - Form BIS-999-Request for Special Priorities Assistance

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 15 Commerce and Foreign Trade 2 2012-01-01 2012-01-01 false Form BIS-999-Request for Special Priorities Assistance I Appendix I to Part 700 Commerce and Foreign Trade Regulations Relating to Commerce... SECURITY INDUSTRIAL BASE REGULATIONS DEFENSE PRIORITIES AND ALLOCATIONS SYSTEM Pt. 700, App. I Appendix...

  17. 15 CFR Appendix I to Part 700 - Form BIS-999-Request for Special Priorities Assistance

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 15 Commerce and Foreign Trade 2 2013-01-01 2013-01-01 false Form BIS-999-Request for Special Priorities Assistance I Appendix I to Part 700 Commerce and Foreign Trade Regulations Relating to Commerce... SECURITY INDUSTRIAL BASE REGULATIONS DEFENSE PRIORITIES AND ALLOCATIONS SYSTEM Pt. 700, App. I Appendix...

  18. 15 CFR Appendix I to Part 700 - Form BIS-999-Request for Special Priorities Assistance

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 15 Commerce and Foreign Trade 2 2011-01-01 2011-01-01 false Form BIS-999-Request for Special Priorities Assistance I Appendix I to Part 700 Commerce and Foreign Trade Regulations Relating to Commerce... SECURITY INDUSTRIAL BASE REGULATIONS DEFENSE PRIORITIES AND ALLOCATIONS SYSTEM Pt. 700, App. I Appendix...

  19. 15 CFR 734.6 - Assistance available from BIS for determining licensing and other requirements.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... commodity, software, technology, or activity is subject to the EAR, or is subject to licensing or other requirements under the EAR, you may ask BIS for an advisory opinion, classification, or a determination whether a particular item or activity is subject to the EAR. In many instances, including those where...

  20. 15 CFR 734.6 - Assistance available from BIS for determining licensing and other requirements.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... commodity, software, technology, or activity is subject to the EAR, or is subject to licensing or other requirements under the EAR, you may ask BIS for an advisory opinion, classification, or a determination whether a particular item or activity is subject to the EAR. In many instances, including those where...

  1. 15 CFR 734.6 - Assistance available from BIS for determining licensing and other requirements.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... commodity, software, technology, or activity is subject to the EAR, or is subject to licensing or other requirements under the EAR, you may ask BIS for an advisory opinion, classification, or a determination whether a particular item or activity is subject to the EAR. In many instances, including those where...

  2. 77 FR 66951 - Proposed Information Collection; Comment Request; BIS Program Evaluation

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-11-08

    ... Bureau of Industry and Security Proposed Information Collection; Comment Request; BIS Program Evaluation... information collections, as required by the Paperwork Reduction Act of 1995. DATES: Written comments must be...., Washington, DC 20230 (or via the Internet at JJessup@doc.gov ). FOR FURTHER INFORMATION CONTACT: Requests...

  3. Study on the Difference of BIS/BAS Scale between Sasang Types

    PubMed Central

    Lee, Soo Jin; Kim, Sung Hye; Lim, Nangyeon; Ahn, Mi Young

    2015-01-01

    Introduction. The purpose of this study was to examine the differences in temperament between So-Yang (SY) and So-Eum (SE) Sasang types using Behavioral Inhibition System/Behavioral Activation System (BIS/BAS) scale to elucidate the biopsychological mechanism underlying the Sasang typology, a traditional Korean personalized medicine. Methods. 248 university students were categorized into three Sasang types, and series of t-tests were conducted, separately for male and female participants, to examine the difference of Behavioral Inhibition System (BIS), Behavioral Activation System (BAS), BAS-Drive (BAS-D), BAS-Fun Seeking (BAS-FS), and BAS-Reward Responsiveness (BAS-RR) scores between SY and SE Sasang types. Results. There were significant differences between Sasang types in the BIS/BAS subscales with consideration of gender. In male participants, BAS-total score of SY type (39.75 ± 4.56) was significantly (t = 2.462, p = 0.016) higher than that of SE type (36.68 ± 4.97). On the other hand, in female participants, BIS score of SY type (20.10 ± 4.01) was significantly (t = −2.097, p = 0.039) lower than that of SE type (21.83 ± 3.91). Discussion. The current study suggested relationship between Sasang typology and Behavior Inhibition and Activation Systems and showed significant differences in BIS/BAS scale between SY and SE Sasang types. Further studies on biological base of Sasang typology are needed. PMID:26681971

  4. Cytotoxic activity of new cerium (III) complexes of bis-coumarins.

    PubMed

    Kostova, Irena; Manolov, Ilia; Momekov, Georgi; Tzanova, Tzvetomira; Konstantinov, Spiro; Karaivanova, Margarita

    2005-12-01

    Complexes of cerium (III) with bis-coumarins: 3,3'-benzylidene-bis(4-hydroxy-2H-1-benzopyran-2-one) and bis(4-hydroxy-2-oxo-2H-chromen-3-yl)-(1H-pyrazol-3-yl)-methane were synthesized by reaction of cerium (III) salt and the ligands, in amounts equal to metal/ligand molar ratio of 1:2. The complexes were prepared by adding an aqueous solution of cerium (III) salt to an aqueous solution of the ligand subsequently raising the pH of the mixture gradually to ca. 5.0 by adding dilute solution of sodium hydroxide. The cerium (III) complexes with bis-coumarins were characterized by different physicochemical methods--elemental analysis, IR-, 1H- and 13C-NMR-spectroscopies and mass-spectral data. The spectral data of cerium (III) complexes were interpreted on the basis of comparison with the spectra of the free ligands. This analysis showed that in the Ce (III) complexes the ligands coordinated to the metal ion through both deprotonated hydroxyl groups. On the basis of the nu(C=O) red shift observed, participation of the carbonyl groups in the coordination to the metal ion was also suggested. Cytotoxic screening by MTT assay was carried out. In the present study we performed comparative evaluation of the cytotoxic effects of the two newly synthesized cerium complexes against the acute myeloid leukemia derived HL-60 and the chronic myeloid leukemia (CML)-derived BV-173. In addition the cytotoxic effects of Ce (III) complex with 3,3'-benzylidene-bis(4-hydroxy-2H-1-benzopyran-2-one) were evaluated on the CML-derived K-562 and LAMA-84 cells, characterized by relative low responsiveness to chemotherapy. The DNA isolated from the cytosolic fraction of BV-173 cells after 24 h treatment with the same complex (at 100 and 200 microM) demonstrated a laddering phenomenon that is indicative for apoptotic cell death.

  5. Defining the Electronic And Geometric Structure of One-Electron Oxidized Copper-Bis-Phenoxide Complexes

    SciTech Connect

    Storr, T.; Verma, P.; Pratt, R.C.; Wasinger, E.C.; Shimazaki, Y.; Stack, T.D.P.

    2009-05-26

    The geometric and electronic structure of an oxidized Cu complex ([CuSal](+); Sal = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with a non-innocent salen ligand has been investigated both in the solid state and in solution. Integration of information from UV-vis-NIR spectroscopy, magnetic susceptibility, electrochemistry, resonance Raman spectroscopy, X-ray crystallography, X-ray absorption spectroscopy, and density functional theory calculations provides critical insights into the nature of the localization/delocalization of the oxidation locus. In contrast to the analogous Ni derivative [NiSal](+) (Storr, T.; et al. Angew. Chem., Int. Ed. 2007, 46, 5198), which exists solely in the Ni(II) ligand-radical form, the locus of oxidation is metal-based for [CuSal](+), affording exclusively a Cu(III) species in the solid state (4-300 K). Variable-temperature solution studies suggest that [CuSal](+) exists in a reversible spin-equilibrium between a ligand-radical species [Cu(II)Sal(*)](+) (S = 1) and the high-valent metal form [Cu(III)Sal](+) (S = 0), indicative of nearly isoenergetic species. It is surprising that a bis-imine-bis-phenolate ligation stabilizes the Cu(III) oxidation state, and even more surprising that in solution a spin equilibrium occurs without a change in coordination number. The oxidized tetrahydrosalen analogue [CuSal(red)](+) (Sal(red) = N,N'-bis(3,5-di- tert-butylhydroxybenzyl)-1,2-cyclohexane-(1R,2R)-diamine) exists as a temperature-invariant Cu(II)-ligand-radical complex in solution, demonstrating that ostensibly simple variations of the ligand structure affect the locus of oxidation in Cu-bis-phenoxide complexes.

  6. Defining the Electronic and Geometric Structure of One-Electron Oxidized Copper–Bis-phenoxide Complexes

    PubMed Central

    Storr, Tim; Verma, Pratik; Pratt, Russell C.; Wasinger, Erik C.; Shimazaki, Yuichi; Stack, T. Daniel P.

    2009-01-01

    The geometric and electronic structure of an oxidized Cu complex ([CuSal]+; Sal = N, N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with a non-innocent salen ligand has been investigated both in the solid state and in solution. Integration of information from UV–vis–NIR spectroscopy, magnetic susceptibility, electrochemistry, resonance Raman spectroscopy, X-ray crystallography, X-ray absorption spectroscopy, and density functional theory calculations provides critical insights into the nature of the localization/delocalization of the oxidation locus. In contrast to the analogous Ni derivative [NiSal]+ (Storr, T.; et al. Angew. Chem., Int. Ed. 2007, 46, 5198), which exists solely in the Ni(II) ligand-radical form, the locus of oxidation is metal-based for [CuSal]+, affording exclusively a Cu(III) species in the solid state (4–300 K). Variable-temperature solution studies suggest that [CuSal]+ exists in a reversible spin-equilibrium between a ligand-radical species [Cu(II)Sal•]+ (S = 1) and the high-valent metal form [Cu(III)Sal]+ (S = 0), indicative of nearly isoenergetic species. It is surprising that a bis-imine–bis-phenolate ligation stabilizes the Cu(III) oxidation state, and even more surprising that in solution a spin equilibrium occurs without a change in coordination number. The oxidized tetrahydrosalen analogue [CuSalred]+ (Salred = N, N′-bis(3,5-di-tert-butylhydroxybenzyl)-1,2-cyclohexane-(1R,2R)-diamine) exists as a temperature-invariant Cu(II)–ligand-radical complex in solution, demonstrating that ostensibly simple variations of the ligand structure affect the locus of oxidation in Cu–bis-phenoxide complexes. PMID:18939830

  7. In vitro reactivation potency of novel symmetrical bis-pyridinium oximes for electric eel acetylcholinesterase inhibited by nerve agent sarin.

    PubMed

    Acharya, Jyotiranjan; Dubey, Devendra Kumar; Kaushik, M P

    2011-12-01

    This communication describes synthesis and in vitro evaluation of a series of novel bis-pyridinium oximes connected by bis-methoxymethyl benzene, 1,4-bis-methoxymethyl (cis)-but-2-ene and 1,4-bis-methoxymethyl but-2-yne linkers as reactivators of sarin inhibited acetylcholinesterase (AChE). The reactivation data of synthesized oximes were compared with those of 2-PAM and obidoxime. The efficacy of oximes such as 1,4-dimethoxy cis-but-2-ene bis-[4,4'-(hydroxyiminomethyl)-pyridinium] dichloride (3g), 1,4-dimethoxy benzene bis-[3,3'-(hydroxyimino-methyl) pyridinium] dichloride (3b) and 1,3-dimethoxy benzene bis-[3,3'-(hydroxy-iminomethyl) pyridinium] dichloride (3e) were found to be more than that of obidoxime in reactivating sarin inhibited AChE. The oxime 3g was able to reactivate 25% of AChE activity in comparison to 20% and 5% reactivation exhibited by 2-PAM and obidoxime respectively at a concentration of 10(-4) M. The pKa of the oximes were determined and correlated with the reactivation potential.

  8. Dechlorination of 1,1,1-Trichloro-2,2-bis(p-chlorophenyl)ethane by Aerobacter aerogenes

    USGS Publications Warehouse

    Wedemeyer, Gary

    1967-01-01

    Whole cells or cell-free extracts of Aerobacter aerogenes catalyze the degradation of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) in vitro to at least seven metabolites: 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE); 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (DDD); 1-chloro-2,2-bis(p-chlorophenyl)ethylene (DDMU); 1-chloro-2,2-bis(p-chlorophenyl)ethane (DDMS); unsym-bis(p-chlorophenyl)ethylene (DDNU); 2,2-bis(p-chlorophenyl)acetate (DDA); and 4,4′-dichlorobenzophenone (DBP). The use of metabolic inhibitors together with pH and temperature studies indicated that discrete enzymes are involved. By use of the technique of sequential analysis, the metabolic pathway was shown to be: DDT → DDD →DDMU →DDMS → DDNU → DDA → DBP, or DDT → DDE. Dechlorination was marginally enhanced by light-activated flavin mononucleotide.

  9. Design and synthesis of novel adenine fluorescence probe based on Eu(III) complexes with dtpa-bis(guanine) ligand.

    PubMed

    Tian, Fengyun; Jiang, Xiaoqing; Dou, Xuekai; Wu, Qiong; Wang, Jun; Song, Youtao

    2017-02-24

    A novel adenine (Ad) fluorescence probe (Eu(III)-dtpa-bis(guanine)) was designed and synthesized by improving experimental method based on the Eu(III) complex and dtpa-bis(guanine) ligand. The dtpa-bis(guanine) ligand was first synthesized by the acylation action between dtpaa and guanine (Gu), and the corresponding Eu(III) complex was successfully prepared through heat-refluxing method with dtpa-bis(guanine) ligand. As a novel fluorescence probe, the Eu(III)-dtpa-bis(guanine) complex can detect adenine (Ad) with characteristics of strong targeting, high specificity and high recognition ability. The detection mechanism of the adenine (Ad) using this probe in buffer solution was studied by ultraviolet-visible (UV-vis) and fluorescence spectroscopy. When the Eu(III)-dtpa-bis(guanine) was introduced to the adenine (Ad) solution, the fluorescence emission intensity was significantly enhanced. However, adding other bases such as guanine (Gu), xanthine (Xa), hypoxanthine (Hy) and uric acid (Ur) with similar composition and structure to that of adenine (Ad) to the Eu(III)-dtpa-bis(guanine) solution, the fluorescence emission intensities are nearly invariable. Meanwhile, the interference of guanine (Gu), xanthine (Xa), hypoxanthine (Hy) and uric acid (Ur) on the detection of the adenine using Eu(III)-dtpa-bis(guanine) probe was also studied. It was found that presence of these bases does not affect the detection of adenine (Ad). A linear response of fluorescence emission intensities of Eu(III)-dtpa-bis(guanine) at 570nm as a function of adenine (Ad) concentration in the range of 0.00-5.00×10(-5)molL(-1) was observed. The detection limit is about 4.70×10(-7)molL(-1).

  10. Design, Synthesis, Characterization and Electrochemical Properties of BODIPY Dyes Containing Mono, Bis-2-Naphthyloxyhexyloxy and 4-(Benzyloxy)Phenoxyhexyloxy Groups.

    PubMed

    Biyiklioglu, Zekeriya; Keleş, Turgut

    2016-11-01

    In this study, the synthesis of boron dipyrromethene dyes containing mono, bis-2-naphthyloxyhexyloxy and 4-(benzyloxy)phenoxyhexyloxy groups has been reported. Boron dipyrromethene dyes were synthesized from the mono, bis-benzaldehyde derivatives with 2,4-dimethylpyrrole in dichloromethane in the presence of trifluoroacetic, 2,3-dichloro-5,6-dicyano-p-benzoquinon, triethyl amine and boron trifluoride diethyl etherate, respectively. Electrochemical characterization of boron dipyrromethene dyes were carried out with voltammetric measurements. Electrochemical studies show that boron dipyrromethene dyes containing mono, bis-2-naphthyloxyhexyloxy and 4-(benzyloxy)phenoxyhexyloxy groups have reversible one reduction potentials unlike irreversible one oxidation potentials. Graphical Abstract ᅟ.

  11. BOOK REVIEW: Meilensteine der Astronomie - Von Aristoteles bis Hawking

    NASA Astrophysics Data System (ADS)

    Duerbeck, H. W.; Hamel, J.

    2006-12-01

    A writer, more specific a writer on the history of astronomy, might from time to time look at the collected document folders with all the research material and reprints, and might wonder: has this been all? Especially at a time when recycling is in vogue? And, perhaps with a request or an invitation to submit something, he or she might consider re-using the material before its definitive disposal. Well, such are my feelings when I looked at Jurgen Hamel's new book Milestones of Astronomy - From Aristoteles to Hawking . A slight chance for survival of medium-sized publishers like Kosmos is to offer popular books, and a title must attract potential buyers: Aristoteles means the "old" times, and as concerns the "mad scientist" of modern times, Stephen Hawking has by now dethroned Einstein. In 1998, Hamel had published a Geschichte der Astronomie - Von den Anfangen bis zur Gegenwart (History of astronomy, from the beginnings to the present), which, of course, he could not simply copy. This time, he selected some stones from his research areas - milestones, touchstones, stumbling blocks in the long road of astronomical evolution - and put them between the covers of his new book. So let us look at these (mile)stones . The reader is informed about Aristoteles on 2 pages, but his medieval interpreter Johannes de Sacrobosco gets 8 pages! Copernicus' life and achievements are described on 9 pages, closely followed by his devotee and translator Rothmann with 8 pages; Copernicus' contemporary, Peter Apian, however, gets about 13! Bessel's and Herschel's lifes and works are described on well-deserved 13 and 15 pages, while the achievements of the two Lucasian professors, Isaac Newton and Stephen Hawking, are just outlined in a single paragraph! Thus, importance is sometimes inversely proportional to text length... But let us become serious now. Why should an active historian outline, for the hundreth time, the life of Copernicus, while there are so many interesting, and often

  12. Mechanistic Diversity in the RuBisCO Superfamily: The Enolase in the Methionine

    SciTech Connect

    Imker,H.; Fedorov, A.; Fedorov, E.; Almo, S.; Gerlt, J.

    2007-01-01

    D-Ribulose 1,5-bisphosphate carboxylase/oxygenase (RuBisCO), the most abundant enzyme, is the paradigm member of the recently recognized mechanistically diverse RuBisCO superfamily. The RuBisCO reaction is initiated by abstraction of the proton from C3 of the D-ribulose 1,5-bisphosphate substrate by a carbamate oxygen of carboxylated Lys 201 (spinach enzyme). Heterofunctional homologues of RuBisCO found in species of Bacilli catalyze the tautomerization ('enolization') of 2,3-diketo-5-methylthiopentane 1-phosphate (DK-MTP 1-P) in the methionine salvage pathway in which 5-methylthio-D-ribose (MTR) derived from 5'-methylthioadenosine is converted to methionine [Ashida, H., Saito, Y., Kojima, C., Kobayashi, K., Ogasawara, N., and Yokota, A. (2003) A functional link between RuBisCO-like protein of Bacillus and photosynthetic RuBisCO, Science 302, 286-290]. The reaction catalyzed by this 'enolase' is accomplished by abstraction of a proton from C1 of the DK-MTP 1-P substrate to form the tautomerized product, a conjugated enol. Because the RuBisCO- and 'enolase'-catalyzed reactions differ in the regiochemistry of proton abstraction but are expected to share stabilization of an enolate anion intermediate by coordination to an active site Mg{sup 2+}, we sought to establish structure-function relationships for the 'enolase' reaction so that the structural basis for the functional diversity could be established. We determined the stereochemical course of the reaction catalyzed by the 'enolases' from Bacillus subtilis and Geobacillus kaustophilus. Using stereospecifically deuterated samples of an alternate substrate derived from D-ribose (5-OH group instead of the 5-methylthio group in MTR) as well as of the natural DK-MTP 1-P substrate, we determined that the 'enolase'-catalyzed reaction involves abstraction of the 1-proS proton. We also determined the structure of the activated 'enolase' from G. kaustophilus (carboxylated on Lys 173) liganded with Mg{sup 2+} and 2

  13. Crystal structure of bis-[2,5-bis-(pyridin-2-yl)-1,3,4-thia-diazole-κ(2) N (2),N (3)]bis-(thio-cyanato-κS)copper(II).

    PubMed

    Laachir, Abdelhakim; Bentiss, Fouad; Guesmi, Salaheddine; Saadi, Mohamed; El Ammari, Lahcen

    2016-08-01

    The mononuclear title complex, [Cu(SCN)2(C12H8N4S)2], was obtained by the reaction of 2,5-bis-(pyridin-2-yl)-1,3,4-thia-diazole and potassium thio-cyanate with copper(II) chloride dihydrate. The copper cation lies on an inversion centre and displays an elongated octa-hedral coordination geometry. The equatorial positions are occupied by the N atoms of two 2,5-bis-(pyridin-2-yl)-1,3,4-thia-diazole ligands, whereas the axial positions are occupied by the S atoms of two thio-cyanate anions. The thia-diazole and the pyridyl rings linked to the metal are approximately coplanar, with a maximum deviation from the mean plane of 0.190 (2) Å. The cohesion of the crystal structure is ensured by weak C-H⋯N hydrogen bonds and π-π inter-actions between parallel pyridyl rings of neighbouring mol-ecules [centroid-to-centroid distance = 3.663 (2) Å], leading to a three-dimensional network.

  14. Crystal structure of bis­[2,5-bis­(pyridin-2-yl)-1,3,4-thia­diazole-κ2 N 2,N 3]bis­(thio­cyanato-κS)copper(II)

    PubMed Central

    Laachir, Abdelhakim; Bentiss, Fouad; Guesmi, Salaheddine; Saadi, Mohamed; El Ammari, Lahcen

    2016-01-01

    The mononuclear title complex, [Cu(SCN)2(C12H8N4S)2], was obtained by the reaction of 2,5-bis­(pyridin-2-yl)-1,3,4-thia­diazole and potassium thio­cyanate with copper(II) chloride dihydrate. The copper cation lies on an inversion centre and displays an elongated octa­hedral coordination geometry. The equatorial positions are occupied by the N atoms of two 2,5-bis­(pyridin-2-yl)-1,3,4-thia­diazole ligands, whereas the axial positions are occupied by the S atoms of two thio­cyanate anions. The thia­diazole and the pyridyl rings linked to the metal are approximately coplanar, with a maximum deviation from the mean plane of 0.190 (2) Å. The cohesion of the crystal structure is ensured by weak C—H⋯N hydrogen bonds and π–π inter­actions between parallel pyridyl rings of neighbouring mol­ecules [centroid-to-centroid distance = 3.663 (2) Å], leading to a three-dimensional network. PMID:27536407

  15. Optical and magneto-optical properties of spin coated films of novel trinuclear bis(oxamato) and bis(oxamidato) type complexes

    NASA Astrophysics Data System (ADS)

    Abdulmalic, Mohammad A.; Fronk, Michael; Bräuer, Björn; Zahn, Dietrich R. T.; Salvan, Georgeta; Eya‧ane Meva, Francois; Rüffer, Tobias

    2016-12-01

    This work reports the first example of the spectroscopic measurements of the Magneto-Optical Kerr Effect (MOKE) of films being composed of trinuclear transition metal complexes on a non-transparent substrate at room temperature. The thin films of the tailor-made trinuclear bis(oxamidato) type complex 5 ([Cu3(opbonPr2)(tmcd)2(NO3)2], opbonPr2 = o-phenylenebis(N'-npropyloxamido, tmcd=trans-(1 R,2 R)-N,N,N‧,N‧-tetramethyl-cyclohexanediamine) and of the bis(oxamato) type complexes 11 ([Cu2Ni(opbaCF3)(pmdta)2(NO3)2], opbaCF3 = 4-trifluoromethyl-o-phenylenebis(oxamato), pmdta = N,N,N,‧N″,N″-pentamethyldiethylenetriamine) and 12 ([Cu3(opba)(bppe)2(NO3)2] (opba = o-phenylenebis(oxamato), bppe = S-N,N-bis(2-picolyl)-1-phenylethylamine) were fabricated by spin-coating and their thicknesses in the range between 0.5 μm and 2 μm was determined by spectroscopic ellipsometry. Based on the spectroscopic ellipsometry results it was also possible to determine the optical constants of the film and compare them with the absorption of the complexes in solution in order to confirm the complex integrity after the film deposition. The fabrication of high-quality films which exhibit Kerr rotation up to 0.2 mrad (11.5 mdeg) was only possible due to tailor-made synthesis, which allows circumventing intermolecular interactions of the trinuclear complexes during the film formation.

  16. Synthesis of the first chiral bidendate bis(trifluoromethyl)phosphane ligand through stabilization of the bis(trifluoromethyl)phosphanide anion in the presence of acetone.

    PubMed

    Hoge, Berthold; Thösen, Christoph; Pantenburg, Ingo

    2006-12-04

    Lewis acid/Lewis base adduct formation of the P(CF3)2- ion and acetone leads to a reduced negative hyperconjugation and, therefore, limits the C--F bond activation. The resulting increased thermal stability of the P(CF3)2- ion in the presence of acetone allows selective substitutions and enables the synthesis of the first example of a chiral, bidentate bis(trifluoromethyl)phosphane ligand: a DIOP derivative, [(2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene)]bis(diphenylphosphane), in which the phenyl groups at the phosphorus atoms are replaced by strong electron-withdrawing trifluoromethyl groups. The resulting high electron-acceptor strength of the synthesized bidentate (CF3)2P ligand is demonstrated by a structural and vibrational study of the corresponding tetracarbonyl-molybdenum complex. The stabilization of the P(CF3)2- ion in the presence of acetone is based on the formation of a dynamic Lewis acid/Lewis base couple, (CF3)2PC(CH3)2O-. Although there is no spectroscopic evidence for the formation of the formulated alcoholate ion, the intermediate formation of (CF3)2PC(CH3)2O- could be proved through the reaction with (CF3)2PP(CF3)2, which yields the novel phosphane-phosphinite ligand (CF3)2PC(CH3)2OP(CF3)2. This ligand readily forms square-planar Pt(II) complexes upon treatment with solid PtCl2.

  17. Spinal mechanisms of antinociceptive effect caused by oral administration of bis-selenide in mice.

    PubMed

    Jesse, Cristiano R; Savegnago, Lucielli; Nogueira, Cristina W

    2008-09-22

    The present study was designed to investigate further the mechanisms involved in the antinociception caused by bis-selenide in behavioral model of pain in mice. Bis-selenide (5-50 mg/kg), given orally, produced significant inhibition of the antinociceptive behavior induced by intrathecal (i.t.) injection of glutamate (175 nmol/site), kainate (110 pmol/site) and (+/-)-1-aminocyclopentane-trans-1,3-dicarboxylic acid (trans-ACPD; 50 nmol/site) and the maximal inhibitions observed were 57+/-5, 46+/-7 and 73+/-3%, respectively. Bis-selenide failed to affect the nociception induced by alpha-amino-3-hydroxy-5-mehtyl-4-isoxazolepropionic acid (AMPA; 135 pmol/site) and N-methyl-d-aspartate (NMDA; 450 pmol/site). This compound also reduced the nociceptive response induced by tumor necrosis factor-alpha (TNF-alpha; 0.1 pg/site), interleukin-1beta (IL-1beta; 1 pg/site), substance P (SP) (135 ng/site, i.t.) and capsaicin (30 ng/site) and the inhibitions observed were 81+/-3%, 88+/-1%, 77+/-3 and 67+/-3, respectively. The oral administration of bis-selenide (25-50 mg/kg) in mice caused a significant increase in the reaction time to thermal stimuli in the hot plate test and the mean ID(50) value (and the 95% confidence limits) was 20.37 (15.00-25.74) mg/kg. The antinociceptive effect caused by bis-selenide (50 mg/kg, p.o.) on the hot plate test in mice was reversed by intrathecal (i.t.) injection of some K(+) channel blockers such as tetraethylammonium (TEA, non-selective voltage-dependent K(+) channel inhibitor) and glibenclamide (ATP-sensitive K(+) channel inhibitor), but not apamin and charybdotoxin (large- and small-conductance Ca(2+)-activated K(+) channel inhibitors, respectively). Together, these results indicate that bis-selenide produces antinociception at spinal sites through the activation of ATP-sensitive and voltage-gated K(+) channels and interaction with kainate and trans-ACDP receptors as well as vanilloid and neuropeptide receptors and pro-inflammatory cytokines.

  18. Cytotoxic activity of new neodymium (III) complexes of bis-coumarins.

    PubMed

    Kostova, Irena; Manolov, Ilia; Momekov, Georgi

    2004-09-01

    Complexes of neodymium (III) with bis-coumarins: 3,3'-benzylidene-bis(4-hydroxy-2H-1-benzopyran-2-one); bis(4-hydroxy-2-oxo-2H-chromen-3-yl)-piridin-2-yl-methane; bis(4-hydroxy-2-oxo-2H-chromen-3-yl)-piridin-4-yl-methane; bis(4-hydroxy-2-oxo-2H-chromen-3-yl)-(1H-pyrazol-3-yl)-methane were synthesized by reaction of neodymium (III) salt and the ligands, in amounts equal to metal:ligand molar ratio of 1:2. The complexes were prepared by adding an aqueous solution of neodymium (III) salt to an aqueous solution of the ligand subsequently raising the pH of the mixture gradually to ca. 5.0 by adding dilute solution of sodium hydroxide. The neodymium (III) complexes with bis-coumarins were characterized by different physicochemical methods-elemental analysis, IR-, (1)H- and (13)C-NMR-spectroscopies and mass-spectral data. The spectral data of neodymium (III) complexes were interpreted on the basis of comparison with the spectra of the free ligands. This analysis showed that in the Nd (III) complexes the ligands coordinated to the metal ion through both deprotonated hydroxyl groups. On the basis of the nu(C=O) red shift observed, participation of the carbonyl groups in the coordination to the metal ion was also suggested. Cytotoxic screening by MTT assay was carried out. The complexes were tested on HL-60, HL-60/Dox and SKW-3 cell lines. The overall results from the preliminary screening program revealed that all of the new Nd (III) complexes reach 50% inhibition of the malignant cells proliferation and thus could be considered as biologically active. On the basis of the IC(50) values obtained compounds Nd(L(1))(OH).H(2)O and Nd(L(3))(OH).2H(2)O were found to exert superior activity in comparison to the remaining complexes.

  19. XANES spectral changes for discotic liquid crystals of bis[1,2-bis(3,4-dioctyloxyphenyl) ethanedione dioximato]Ni(II)

    NASA Astrophysics Data System (ADS)

    Yokomizo, Mitsutoshi; Kurisaki, Tsutomu; Yamaguchi, Toshio; Wakita, Hisanobu; Oka-Inagaki, Yoshio; Ohta, Kazuchika

    The one-dimensional stacking structures of a liquid crystal Ni complex- [1,2-bis(3,4-dialkoxyphenyl)ethanedione dioximato]Ni(II), [Ni{(C8O)4dpg}2],which shows thermochromism, (see Fig. 1) have been investigated over a temperature range from room temperature to 220°C by analyzing X-ray absorption near-edge structure (XANES) spectra together with a DV-X[alpha] molecular orbital calculation. The thermochromic character of the complex is discussed through the structural change with temperature in Ni--Ni and Ni to ligand atom interactions.

  20. Di-μ-chlorido-bis-{aqua-chlorido[2,2'-thio-bis(pyridine N-oxide)-κO]copper(II)}.

    PubMed

    Seidel, Rüdiger W; Oppel, Iris M

    2009-03-28

    The crystal structure of the title compound, [Cu(2)Cl(4)(C(10)H(8)N(2)O(2)S)(2)(H(2)O)(2)], comprises neutral centrosymmetric μ-chloride-bridged dinuclear units. Each Cu(II) ion is penta-coordinated by three chloride ligands, a pyridine N-oxide O atom and a water mol-ecule. Intra- and inter-molecular O-H⋯O hydrogen bonds occur between the coordinated water mol-ecules and the uncoordinated and coordinated pyridine N-oxide groups of the 2,2'-thio-bis(pyridine N-oxide) ligands, respectively.