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Sample records for 2-acetylpyridine n4-phenyl thiosemicarbazone

  1. 2-Acetylpyridine N4-Phenyl- Thiosemicarbazone as a new tool for tumour diagnosis

    The aim of this work was to determine in vivo biodistribution of radiolabelled 2-acetylpyridine N4 phenyl thiosemicarbazone (Ph) and to evaluate its applicability for tumour diagnosis. Ph was labelled with 125I using lactoperoxidase method and radiochemical analysis was performed by chromatography. 125I-Ph production was successful with 86 ± 9.2% of radiochemical purity and high specific activity (17.6 TBq /mmol). 125I-Ph was used for biodistribution and pharmacokinetics studies on Swiss mice bearing Ehrlich solid tumour. 125I-Ph presented a rapid blood clearance (T1/2= 97.2 min.) and the kidneys were the main excretion pathway (CL0.01 mL/min). 125I-Ph uptake was significant in tumour (2.5%ID/g) and tumour-to-normal tissue uptake was more than 20-fold higher depending on the organ. The uptake by the organs like heart, lungs, stomach and liver followed the blood perfusion. Our results suggest that 125I-Ph possess indispensable characteristics for an efficient radiopharmaceutical for tumour diagnosis. The next step will be to evaluate the quality of tumour SPECT images provided by 131I-Ph. (author)

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

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

    2009-07-01

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

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

    Despite the wide range of antineoplastic agents available, resistance of some types of cancer and toxicity to normal cells have been identified as the main causes of treatment failure and death. The lack of early and precise diagnosis is also responsible for reducing survival of cancer patients. In this context, the development of substances with low toxicity and therapeutic potential and/or diagnosis purpose, is the major tool in an attempt to increase the survival of patients and assure the safety and efficacy of treatment. Thiosemicarbazones (TSC) are a class of synthetic compounds that have several biological activities, including antitumor. Although several studies have shown the great potential of TSC as therapeutic and / or diagnostic agents, different chemical modifications performed on this class of molecules indicate new possibilities for applications and still require further studies. The objective of this study was to evaluate the potential applicability of 2-acetylpyridine N-4-phenyl thiosemicarbazones derivatives for cancer therapy and diagnosis. The results showed that all 13 TSC tested were cytotoxic to breast and glioblastoma tumor cell lines, presenting higher in vitro antitumor activity than etoposide, an antineoplastic and inhibitor of topoisomerase II frequently used for cancer therapy. The TSC that have halogen or nitro on ortho position showed higher antitumor activity in vitro than their isomers with halogen or nitro on meta or para position of the phenyl group. H2Ac4oFPh and H2Ac4oClPh compounds showed the highest antitumor activity among all tested compounds, with IC50 in nanomolar order. These TSC induced cell death by apoptosis and oxidative stress was responsible, at least in part, for this type of cell death. The 5 mg.kg-1 H2Ac4oFPh dose, administered s.c., for 4 consecutive days, did not induce important toxicity; however, the same treatment protocol was not effective for tumor growth reduction in an animal model of brain tumor

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

    Soares, Marcella Araugio

    2013-08-01

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

  5. Preparation of [61Cu]-2-acetylpyridine thiosemicarbazone complex as a possible PET tracer for malignancies

    Due to the interesting anti-proliferative properties of copper-thiosemicarbazone complexes, the production of a 61Cu-labeled thiosemicarbazone, i.e. 2-acetylpyridine thiosemicarbazone (APTS) was investigated. Copper-61 (T1/2=3.33h) was produced via the 64Zn(p,α)61Cu nuclear reaction using a natural zinc target irradiated with 22MeV protons for 500μAh. The 61Cu was separated from the irradiated target material by a two-step method and converted to acetate; this yielded a final activity of 222GBq (6.0Ci), with a radiochemical yield of >95%. The 61Cu-acetate was mixed with 2-acetylpyridine thiosemicarbazone for 30min at room temperature to yield [61Cu]APTS with a radiochemical yield of more than 80%. Colorimetric methods showed that residual chemical impurities in the product were below the accepted limits. Radio thin layer chromatography (RTLC) showed a radiochemical purity of more than 99% after C18 column chromatography. A specific activity of about 370-740MBq/mmol (10-20Ci/mmol) was obtained. The stability of the final product was checked in the absence and presence of human serum at 37oC for up to 3h. The partition coefficient of the final complex was also determined

  6. Preparation of [{sup 61}Cu]-2-acetylpyridine thiosemicarbazone complex as a possible PET tracer for malignancies

    Jalilian, A.R. [Cyclotron and Nuclear Medicine Department, Nuclear Research Center for Agriculture and Medicine (NRCAM), Atomic Energy Organization of Iran, Moazzen Boulevard, Rajaeeshahr, P.O. Box 31485-498 Karaj (Iran, Islamic Republic of)]. E-mail: ajalilian@nrcam.org; Rowshanfarzad, P. [Cyclotron and Nuclear Medicine Department, Nuclear Research Center for Agriculture and Medicine (NRCAM), Atomic Energy Organization of Iran, Moazzen Boulevard, Rajaeeshahr, P.O. Box 31485-498 Karaj (Iran, Islamic Republic of); Sabet, M. [SSDL and Health Physics Department, Nuclear Research Center for Agriculture and Medicine (NRCAM), Atomic Energy Organization of Iran, Moazzen Boulevard, Rajaeeshahr, P.O. Box 31485-498 Karaj, Iran. (Iran); Shafiee, A. [Faculty of Pharmacy and Pharmaceutical Sciences Research center, Tehran University of Medical Sciences, P.O. Box 14155-6451 Tehran (Iran, Islamic Republic of)

    2006-03-15

    Due to the interesting anti-proliferative properties of copper-thiosemicarbazone complexes, the production of a {sup 61}Cu-labeled thiosemicarbazone, i.e. 2-acetylpyridine thiosemicarbazone (APTS) was investigated. Copper-61 (T{sub 1/2}=3.33h) was produced via the {sup 64}Zn(p,{alpha}){sup 61}Cu nuclear reaction using a natural zinc target irradiated with 22MeV protons for 500{mu}Ah. The {sup 61}Cu was separated from the irradiated target material by a two-step method and converted to acetate; this yielded a final activity of 222GBq (6.0Ci), with a radiochemical yield of >95%. The {sup 61}Cu-acetate was mixed with 2-acetylpyridine thiosemicarbazone for 30min at room temperature to yield [{sup 61}Cu]APTS with a radiochemical yield of more than 80%. Colorimetric methods showed that residual chemical impurities in the product were below the accepted limits. Radio thin layer chromatography (RTLC) showed a radiochemical purity of more than 99% after C{sub 18} column chromatography. A specific activity of about 370-740MBq/mmol (10-20Ci/mmol) was obtained. The stability of the final product was checked in the absence and presence of human serum at 37{sup o}C for up to 3h. The partition coefficient of the final complex was also determined.

  7. Preparation and biodistribution studies of [67Ga]2-acetylpyridine 4,4-dimethyl thiosemicarbazone complex as a possible SPECT tracer for detection of malignancies

    Due to the interesting anti-proliferative properties of gallium-thiosemicarbazone complexes, the production of [67Ga]labeled 2-acetylpyridine 4,4- dimethyl thiosemicarbazone (APTSM2) was investigated. The freshly prepared [67Ga]GaCl3 was mixed with 2-acetylpyridine 4,4-dimethyl thiosemicarbazone for 60 minutes at 90 deg C to yield [67Ga]APTSM2 with a radiochemical yield of more than 98%. Radio-thin-layerchromatography (RTLC) showed a radiochemical purity of more than 99%. A specific activity of about 370-740 MBq/mmol (10-20 Ci/mmol) was obtained. The stability of the final product was checked in the absence and presence of human serum at 37 deg C. The partition coefficient of the final complex was also determined. The biodistribution of the labeled compound in normal rats was compared with that of free Ga3+ cation up to 22 hours. (author)

  8. Ruthenium(II) complexes containing N(4)-tolyl-2-acetylpyridine thiosemicarbazones and phosphine ligands: NMR and electrochemical studies of cis- trans isomerization

    Graminha, Angelica E.; Batista, Alzir A.; Ellena, Javier; Castellano, Eduardo E.; Teixeira, Letícia R.; Mendes, Isolda C.; Beraldo, Heloisa

    2008-03-01

    [Ru(HL)(PPh 3) 2Cl]Cl complexes have been obtained in which HL = N(4)- ortho (complex 1), N(4)- meta (complex 2) and N(4)- para-tolyl 2-acetylpyridine thiosemicarbazone (complex 3). NMR and electrochemical studies indicate that both cis and trans isomers exist in solution, and that the cis isomers are converted into the trans isomers with time. Crystal structure determination of ( 1) reveals that the trans isomer is formed in the solid state.

  9. Development of [103Pd]-2-acetylpyridine 4N-methyl thiosemicarbazone complex for targeted therapy

    Due to interesting biological properties of palladium-thiosemicarbazono complexes, production of a 103Pd-labeled anti-cancer complex, i.e., [103Pd]-2-acetylpyridine 4N-methylthiosemicarbazone ([103Pd]-APMTS) was developed. Palladium-103 (T1/2 = 16.96 d) produced via the 103Rh(p,n)103Pd nuclear reaction using natural rhodium target, was separated from the irradiated target material. Proton energy was 18 MeV with 200 μA irradiation for 15 hours (final activity 700 mCi of 103Pd2+, RCY>95%, radionuclidic purity>99%). The final activity was eluted in form of Pd(NH3)2Cl2 in order to react with 2-acetylpyridine-4N-methylthiosemicarbazone to yield [103Pd]-APMTS. Chemical purity of the final product was confirmed to be within the accepted limits by polarography. [103Pd]-APMTS was prepared with a radiochemical yield of more than 80% at room temperature after 3 hours. The labeling reaction was optimized for time, temperature and radioactivity and ligand ratio. A mixture of APMTS and Pd activity in ethanol was heated at 90 deg C for 3 hours followed by reverse phase SPE purification using C18 plus Sep-Pak. Radiochemical purity of more than 99% using RTLC and specific activity of about 12500 Ci/mol was obtained. The stability of the tracer was checked in the final product and the presence of human serum at 37 deg C up to 3 hours. The partition coefficient of the final complex was determined by octanol:saline buffer distribution. (author)

  10. Spectrophotometric analysis of Cis-platin injection and Lead containing cosmetics using 2-acetylpyridine-4 - phenyl -3- thiosemicarbazone as complexing reagent

    The reaction of reagent 2- acetylpyridine - 4 - phenyl -3 -thiosemicarbazone (APPT) was examined towards platinum (ii), gold (III), vanadium (V), ruthenium (IV), Tellurium (VI), arsenic (III) and lead (II) spectrophotometrically. The reaction were carried out in slightly acidic to neutral media and indicated molar absorptivity in range 9.6 x 10/sup 2/ to 2.2 x 10/sup 4/ L. mole/sup -1/ cm/sup -1/ between 370 to 435 nm. Each of the complex obeyed the beer's Law. The method was used for analysis of anticancer drug cis-platin and cosmetic (Surma) for the contents of platinum (II) and lead (II) respectively. (author)

  11. Characterization of copper(II) complexes of N4, N4-disubstituted thiosemicarbazones of 2-acetylpyridine by combined evaluation of electronic and ESR parameters

    Jain, Satendra K.; Garg, Bhagwan S.; Bhoon, Yudhvir K.

    Copper(II) complexes of 2-acetylpyridine 4,4-dimethyl-3-thiosemicarbazone (L'H) and 2-acetylpyridine 4-(4-methylpiperidinyl)-3-thiosemicarbazone (LH) of the general formula CuLX (where L is a deprotonated ligand and X = F -, Cl -, Br -, I -, OAc - and NO -3) have been synthesized and characterized by elemental analysis, magnetic susceptibility measurements between 93 and 298 K in the polycrystalline state, i.r. spectra, electronic spectra, conductivity measurements and ESR spectra recorded in the polycrystalline state, in chloroform and dimethylformamide solution at room temperature and at 77K. The molar conductivities measured in dimethylformamide for all complexes show them to be non-electrolytes. The terdentate character of the ligands in all the complexes is inferred from i.r. spectral studies. The i.r. spectra also confirm the monodentate nature of the polyatomic anions such as nitrate and acetate. The electronic spectra in Nujol mulls, chloroform or dimethylformamide solution suggest planar geometry for all of the complexes. The calculated ESR parameters show an axial dx2- y2 ground state and suggest coordination through sulphur in agreement with the i.r. results. Little change in the value of g with temperature indicates no significant change in planarity of these four coordinated species. ESR spectra in solution at room temperature and 77 K also suggest a strong covalent environment with strong in-plane sigma and pi bonds provided by the ligands.

  12. Synthesis, molecular structure, spectral analysis, natural bond order and intramolecular interactions of 2-acetylpyridine thiosemicarbazone: A combined DFT and AIM approach

    Singh, Ravindra Kumar; Singh, Ashok Kumar

    2015-08-01

    2-Acetylpyridine thiosemicarbazone was synthesized and characterized by elemental analysis, 1H, 13C NMR, IR, UV and ESI-MS mass spectrometry. Quantum chemical calculations have been performed at DFT level of theory using B3LYP functional and 6-31G (d, p) as basis set. Potential energy distribution (PED) for the normal modes of vibrations was done using Gar2ped program. The time dependent density functional theory (TD-DFT) was used to assign the various electronic transitions within molecule in gas as well as solvent phase. Non linear optical (NLO) behavior of title compound was investigated by the computed value of first hyperpolarizability (β0). Stability of molecule as a result of hyperconjugative interactions and electron delocalization was analyzed using NBO analysis. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. Intramolecular interactions were analyzed by AIM approach. The chemical reactivity descriptors were calculated to study the reactive sites within molecule.

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

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

  14. Synthesis, characterization and crystal structure of cobalt(III) complexes containing 2-acetylpyridine thiosemicarbazones: DNA/protein interaction, radical scavenging and cytotoxic activities.

    Manikandan, Rajendran; Viswanathamurthi, Periasamy; Velmurugan, Krishnaswamy; Nandhakumar, Raju; Hashimoto, Takeshi; Endo, Akira

    2014-01-01

    The synthesis, structure and biological studies of cobalt(III) complexes supported by NNS-tridentate ligands are reported. Reactions of 2-acetylpyridine N-substituted thiosemicarbazone (HL(1-3)) with [CoCl2(PPh3)2] resulted [Co(L(1-3))2]Cl (1-3) which were characterized by elemental analysis and various spectral studies. The molecular structure of the complex 1 has been determined by single crystal X-ray diffraction studies. In vitro DNA binding studies of complexes 1-3 carried out by fluorescence studies and the results revealed the binding of complexes to DNA via intercalation. The binding constant (Kb) values of complexes 1-3 from fluorescence experiments showed that the complex 3 has greater binding propensity for DNA. The DNA cleavage activity of the complexes 1 and 3 were ascertained by gel electrophoresis assay which revealed that the complexes are good DNA cleavage agents. Further, the interactions of the complexes with bovine serum albumin (BSA) were also investigated using fluorescence spectroscopic method, which showed that the complexes 1-3 could bind strongly with BSA. The antioxidant property of the complexes was evaluated to test their free-radical scavenging ability. Furthermore, in vitro cytotoxicity of the complexes against MCF-7 and A431 cell lines was assayed which showed higher activity and efficiently vanished the cancer cells even at low concentrations. PMID:24342132

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

    Thiosemicarbazones have attracted great pharmacological interest because of their biological properties, such as cytotoxic activity against multiple strains of human tumors. The most studied compounds are pyridine-based because of their resemblance to pyridoxal metabolites that attach to co-enzyme B6-dependant enzymes. This work aimed the characterization of the anti tumoral effect of N(4)-methyl-tolyl-2-acetylpyridine and 2-pyridinoformamide-derived thiosemicarbazones and the development of a radiopharmaceutical based on a thiosemicarbazone metal complex for positron emission tomography. In the first phase of this study were synthesized twenty-one thiosemicarbazones, derived from N(4)methyl-2 acetylpyridine and 2-pyridine formamide, as well as their metal complexes (Sn, Ga and Cu). Their cytotoxic potential were evaluated against brain and breast tumor cells in vitro. Our results showed all of them presented powerful cytotoxic and antiproliferative activities against glioblastoma multiform and breast adenocarcinoma at very low concentrations (nanomolar range). Morphological alterations characteristic of apoptosis, such as cell shrinkage, chromatin condensation were observed. Copper chloride was used as control and has presented IC50 at millimolar range suggesting that copper complexation with thiosemicarbazone significantly increases (more than 1 million) the anti tumoral effect of this metal. Due to the potent anti tumoral activity of N(4)-methyl-tolyl-2-acetylpyridine derived thiosemicarbazones and the excellent properties of 64Cu (T1/2 = 12.7 hours, β+, β-, and EC decay), at the second part for this work it was developed a new imaging agent (radiopharmaceutical) for tumor detection by positron emission tomography (PET). The radiopharmaceuticals were produced in the nuclear reactor TRIGA-IPR-R1 from CDTN, via neutron capture reaction 63Cu (n,γ) 64Cu, of the copper complex N(4)-ortho-toluyl-2-acetylpyridine thiosemicarbazone (Culac). The induced specific

  16. Structural and spectral studies of an iron(III) complex [Fe(Pranthas) 2][FeCl 4] derived from 2-acetylpyridine- N(4), N(4)-(butane-1, 4-diyl) thiosemicarbazone (HPranthas)

    Sreekanth, A.; Fun, Hoong-Kun; Prathapachandra Kurup, M. R.

    2005-02-01

    A novel iron(III) complex of 2-acetylpyridine N(4), N(4)-(butyl-1, 4-diyl) thiosemicarbazone (HPranthas), [Fe(Pranthas) 2]FeCl 4 was synthesized and physico-chemically characterized by means of partial elemental analysis, magnetic measurements (polycrystalline state), UV-Vis and IR spectroscopies. The presence of spin-paired iron(III) cation with dxz2dyz2dxy1 ground state is revealed by the EPR and Mössbauer spectral data. Structure of the free ligand HPranthas and the complex [Fe(Pranthas) 2]FeCl 4 were solved by single crystal X-ray diffraction. The framework of iron(III) complex consists of a discrete monomeric cationic entity containing low spin iron(III) in a slightly distorted octahedral environment. The metal ion is bonded to one sulfur and two nitrogens of each thiosemicarbazone molecule. The tetrachloroferrate(III) ion acts as counterion.

  17. Palladium(II) complexes with thiosemicarbazones: syntheses, characterization and cytotoxicity against breast cancer cells and Anti-Mycobacterium tuberculosis activity

    Maia, Pedro I. da S.; Deflon, Victor M., E-mail: deflon@iqsc.usp.b [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Inst. de Quimica; Graminha, Angelica; Batista, Alzir A. [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Dept. de Quimica; Pavan, Fernando R.; Leite, Clarice Q.F. [UNESP, Araraquara, SP (Brazil). Faculdade de Ciencias Farmaceuticas; Back, Davi F.; Lang, Ernesto S. [Universidade Federal de Santa Maria (UFSM), RS (Brazil). Dept. de Quimica; Ellena, Javier [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Inst. de Fisica; Lemos, Sebastiao de S. [Universidade de Brasilia (UnB), DF (Brazil). Inst. de Quimica; Salistre-de-Araujo, Heloisa S. [Universidade Federal de Sao Carlos (UFSCAR), SP (Brazil). Dept. de Ciencias Fisiologicas

    2010-07-01

    Three Pd{sup II} complexes were prepared from N(4)-substituted thiosemicarbazones: [Pd(aptsc)(PPh{sub 3})](NO{sub 3}) centre dot H{sub 2}O, 1, [Pd(apmtsc)(PPh{sub 3})](NO{sub 3}), 2, and [Pd(apptsc)(PPh{sub 3})](NO{sub 3}) centre dot H{sub 2}O, 3, where PPh{sub 3} = triphenylphosphine; Haptsc 2-acetylpyridine-thiosemicarbazone; Hapmtsc 2-acetylpyridine-N(4)-methyl-thiosemicarbazone and Happtsc 2-acetylpyridine-N(4)-phenyl-thiosemicarbazone. All complexes were characterized by elemental analysis, IR, UV-Vis, {sup 1}H and {sup 31}P{l_brace}{sup 1}H{r_brace} NMR spectroscopies, and had their crystalline structures determined by X-ray diffractometry from single crystals. The monoanionic thiosemicarbazonate ligands act in a tridentate mode, binding to the metal through the pyridine nitrogen, the azomethine nitrogen and the sulfur atoms. The cytotoxic activity against the breast cancer cell line MDA-MB231 and the anti-Mycobacterium tuberculosis H{sub 37}Rv ATCC 27294 activity were evaluated for the compounds. All Pd{sup II} complexes were highly active against the studied cell line, presenting similar values of IC{sub 50}, around 5 mumol L{sup -1}, while the clinically applied antitumor agent cisplatin was inactive. The compounds show remarkable anti-M. tuberculosis activities, presenting MIC values comparable or better than some commercial anti-M tuberculosis drugs. (author)

  18. Palladium(II) complexes with thiosemicarbazones: syntheses, characterization and cytotoxicity against breast cancer cells and Anti-Mycobacterium tuberculosis activity

    Three PdII complexes were prepared from N(4)-substituted thiosemicarbazones: [Pd(aptsc)(PPh3)](NO3) · H2O, 1, [Pd(apmtsc)(PPh3)](NO3), 2, and [Pd(apptsc)(PPh3)](NO3) · H2O, 3, where PPh3 = triphenylphosphine; Haptsc 2-acetylpyridine-thiosemicarbazone; Hapmtsc 2-acetylpyridine-N(4)-methyl-thiosemicarbazone and Happtsc 2-acetylpyridine-N(4)-phenyl-thiosemicarbazone. All complexes were characterized by elemental analysis, IR, UV-Vis, 1H and 31P{1H} NMR spectroscopies, and had their crystalline structures determined by X-ray diffractometry from single crystals. The monoanionic thiosemicarbazonate ligands act in a tridentate mode, binding to the metal through the pyridine nitrogen, the azomethine nitrogen and the sulfur atoms. The cytotoxic activity against the breast cancer cell line MDA-MB231 and the anti-Mycobacterium tuberculosis H37Rv ATCC 27294 activity were evaluated for the compounds. All PdII complexes were highly active against the studied cell line, presenting similar values of IC50, around 5 μmol L-1, while the clinically applied antitumor agent cisplatin was inactive. The compounds show remarkable anti-M. tuberculosis activities, presenting MIC values comparable or better than some commercial anti-M tuberculosis drugs. (author)

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

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

    2011-07-01

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

  20. 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

    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.

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

    Silva, Paulo Roberto Ornelas da

    2008-07-01

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

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

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

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

    Vilas Boas, Fabricio A.S.; Hudson, Luiza O.; Santos, Raquel G. dos [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil). Lab. de Radiobiologia], e-mail: fasvb@cdtn.br, e-mail: luluhud@yahoo.com.br, e-mail: santosr@cdtn.br; Mendes, Isolda C.; Beraldo, Heloisa O. [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Quimica], e-mail: Isolda.mendes@terra.com.br, e-mail: hberaldo@pq.cnpq.br

    2009-07-01

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

  4. Synthesis and structural characterization of biologically active metal complexes of N1-(N-morpholinoacetyl)-N4-phenyl thiosemicarbazide and 3,4-methylenedioxybenzaldehyde thiosemicarbazone with oxovanadium(IV) chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), cadmium(II), uranium(VI), thorium(IV) and silicon(IV)

    The chelating behaviour of N1-(N-morpholinoacetyl)-N4-phenyl thiosemicarbazide (MPTSC) and 3,4-methylenedioxybenzaldehyde thiosemicarbazone (MDBT) towards oxovanadium(IV), Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Cd(II), dioxouranium(VI), Th(IV) and Si(IV) has been investigated on the basis of elemental analysis, molar conductance, magnetic susceptibility, electronic, infrared, 1H NMR, ESR, thermal and Moessbauer studies. The above studies indicate that MPTSC acts as monobasic bidentate O, S donor towards oxovanadium(IV), Co(II), Ni(II), and Si(IV); monobasic bidentate N, S donor towards Cd(II) and monobasic tridentate O; N, S donor towards Cu(II) and Th(IV), while MDBT acts as neutral bidentate N,S donor towards oxovanadium(IV), Cr(III), Mn(II), Fe(III), dioxouranium(VI) and Th(IV). The ligands and their metal complexes have been screened in vitro for antibacterial and antifungal activities. The results indicate that in some complexes biocidal activity of ligand increases on complexation. (author). 32 refs., 1 fig., 1 tab

  5. Structural studies of six and four coordinate zinc(II), nickel(II) and dioxovanadium(V) complexes with thiosemicarbazones

    Sreekanth, A.; Sivakumar, S.; Prathapachandra Kurup, M. R.

    2003-07-01

    Three Zn(II) complexes of di-2-pyridyl ketone thiosemicarbazone, an octahedral Ni(II) complex of 2-acetylpyridine hexamethyleneiminyl-3-thiosemicarbazone, and a V(V) complex of 2-acetylpyridine morpholyl-3-thiosemicarbazone were prepared and characterized. Crystal structure of Ni(II) and V(V) complexes are reported. The ligand in the nickel complex is found to coordinate in the thione form with a pseudo octahedral geometry and the vanadium(V) complex has trigonal bipyramidal geometry.

  6. Novel Mechanism of Cytotoxicity for the Selective Selenosemicarbazone, 2-Acetylpyridine 4,4-Dimethyl-3-selenosemicarbazone (Ap44mSe): Lysosomal Membrane Permeabilization.

    Al-Eisawi, Zaynab; Stefani, Christian; Jansson, Patric J; Arvind, Akanksha; Sharpe, Philip C; Basha, Maram T; Iskander, George M; Kumar, Naresh; Kovacevic, Zaklina; Lane, Darius J R; Sahni, Sumit; Bernhardt, Paul V; Richardson, Des R; Kalinowski, Danuta S

    2016-01-14

    Selenosemicarbazones show marked antitumor activity. However, their mechanism of action remains unknown. We examined the medicinal chemistry of the selenosemicarbazone, 2-acetylpyridine 4,4-dimethyl-3-selenosemicarbazone (Ap44mSe), and its iron and copper complexes to elucidate its mechanisms of action. Ap44mSe demonstrated a pronounced improvement in selectivity toward neoplastic relative to normal cells compared to its parent thiosemicarbazone. It also effectively depleted cellular Fe, resulting in transferrin receptor-1 up-regulation, ferritin down-regulation, and increased expression of the potent metastasis suppressor, N-myc downstream regulated gene-1. Significantly, Ap44mSe limited deleterious methemoglobin formation, highlighting its usefulness in overcoming toxicities of clinically relevant thiosemicarbazones. Furthermore, Cu-Ap44mSe mediated intracellular reactive oxygen species generation, which was attenuated by the antioxidant, N-acetyl-L-cysteine, or Cu sequestration. Notably, Ap44mSe forms redox active Cu complexes that target the lysosome to induce lysosomal membrane permeabilization. This investigation highlights novel structure-activity relationships for future chemotherapeutic design and underlines the potential of Ap44mSe as a selective anticancer/antimetastatic agent. PMID:26645570

  7. [{sup 67}Ga]Gallium-complex with 2-acetylpyridine N4-ortho fluorophenylthiosemicarbazone as a radiotracer for brain tumor diagnosis

    Pesquero, Jorge L. [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Fisiologia e Biofisica; Pujatti, Priscilla B.; Araujo, Elaine B. de [Instituto de Pesquisas Energeticas Nucleares (DIRF/IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Diretoria de Radiofarmacia; Lessa, Josane A.; Beraldo, Heloisa [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Quimica; Soares, Marcella A.; Santos, Raquel G. dos, E-mail: santosr@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

    2011-07-01

    The aim of this work was to develop a {sup 67}Ga-based SPECT imaging agent derived from 2-acetylpyridine N4-orthofluorophenyl - thiosemicarbazone (PhoF). For this purpose, PhoF was radiolabeled using {sup 67}Ga as radiotracer, and after quality control analysis its biodistribution and SPECT imaging were evaluated on Swiss mice and Nude mice bearing glioblastoma multiform tumor (U87-MG). The labelling of PhoF with {sup 67}GaCl{sub 3} was performed in methanol for 30 minutes at room temperature. Radiochemical analyses were done by HPLC with radioactivity detection. {sup 67}Ga- PhoF was successful produced with 97.5 {+-} 0.6% of radiochemical purity and high specific activity (1.0 TBq /mmol). {sup 67}Ga- PhoF showed to be a stable compound keeping its stability, when stored at 2-4 deg C. In biodistribution studies, {sup 67}Ga- PhoF displayed not only a significant tumor uptake, but also rapid blood clearance (T{sub 1/2} {sub fast} {sub phase}= 3.7 min. and T{sub 1/2} {sub slow} {sub phase}= 127.2 min.) and low accumulations in non target tissues, resulting in high target-to-non target ratios. Scintigraphic images of {sup 67}Ga- PhoF in nude mice bearing U87-MG tumor showed a significant activity in tumor ({approx} 7% of total activity) and tumor-to-normal tissue ratio was more than 10-fold higher depending on the organ. Our results suggest that {sup 67}Ga-PhoF possess indispensable characteristics for a good radiopharmaceutical for brain tumor diagnosis. (author)

  8. [67Ga]Gallium-complex with 2-acetylpyridine N4-ortho fluorophenylthiosemicarbazone as a radiotracer for brain tumor diagnosis

    The aim of this work was to develop a 67Ga-based SPECT imaging agent derived from 2-acetylpyridine N4-orthofluorophenyl - thiosemicarbazone (PhoF). For this purpose, PhoF was radiolabeled using 67Ga as radiotracer, and after quality control analysis its biodistribution and SPECT imaging were evaluated on Swiss mice and Nude mice bearing glioblastoma multiform tumor (U87-MG). The labelling of PhoF with 67GaCl3 was performed in methanol for 30 minutes at room temperature. Radiochemical analyses were done by HPLC with radioactivity detection. 67Ga- PhoF was successful produced with 97.5 ± 0.6% of radiochemical purity and high specific activity (1.0 TBq /mmol). 67Ga- PhoF showed to be a stable compound keeping its stability, when stored at 2-4 deg C. In biodistribution studies, 67Ga- PhoF displayed not only a significant tumor uptake, but also rapid blood clearance (T1/2fastphase= 3.7 min. and T1/2slowphase= 127.2 min.) and low accumulations in non target tissues, resulting in high target-to-non target ratios. Scintigraphic images of 67Ga- PhoF in nude mice bearing U87-MG tumor showed a significant activity in tumor (∼ 7% of total activity) and tumor-to-normal tissue ratio was more than 10-fold higher depending on the organ. Our results suggest that 67Ga-PhoF possess indispensable characteristics for a good radiopharmaceutical for brain tumor diagnosis. (author)

  9. Organotin(IV) complexes with 2-acetylpyridine benzoyl hydrazones: antimicrobial activity

    Despaigne, Angel A.R.; Vieira, Lorena F.; Mendes, Isolda C.; Costa, Fernanda B. da; Beraldo, Heloisa, E-mail: hberaldo@ufmg.b [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Quimica; Speziali, Nivaldo L. [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Fisica

    2010-07-01

    Reaction of n-butyltin trichloride, [Bu{sup n}SnCl{sub 3}], and phenyltin trichloride, [PhSnCl{sub 3}], with 2-acetylpyridine benzoyl hydrazone (H2AcPh), 2-acetylpyridine para-chloro-benzoyl hydrazone (H2AcpClPh) and 2-acetylpyridine para-nitro-benzoyl hydrazone (H2AcpNO{sub 2}Ph) gave [Bu{sup n}Sn(2AcPh)Cl{sub 2}] (1), [Bu{sup n}Sn(2AcpClPh)Cl{sub 2}] (2), [Bu{sup n}Sn(2AcpNO{sub 2}Ph)Cl{sub 2}] (3), [PhSn(2AcPh)Cl{sub 2}] (4), [PhSn(2AcpClPh)Cl{sub 2}] (5) and [PhSn(2AcpNO{sub 2}Ph)Cl{sub 2}] (6) as products. Among the hydrazones H2AcpClPh proved to be the most active against Staphylococcus aureus and Candida albicans. Upon coordination the antibacterial activity of both tin and the hydrazones significantly increases. Complexes 2 and 5 revealed to be the most active as antimicrobial agents. (author)

  10. Metal complexes with 2-acetylpyridine-N(4)-orthochlorophenylthiosemicarbazone: cytotoxicity and effect on the enzymatic activity of thioredoxin reductase and glutathione reductase.

    Parrilha, Gabrieli L; Ferraz, Karina S O; Lessa, Josane A; de Oliveira, Kely Navakoski; Rodrigues, Bernardo L; Ramos, Jonas P; Souza-Fagundes, Elaine M; Ott, Ingo; Beraldo, Heloisa

    2014-09-12

    Metal complexes with 2-acetylpyridine-N(4)-orthochlorophenylthiosemicarbazone (H2Ac4oClPh) were assayed for their cytotoxicity against MCF-7 breast adenocarcinoma and HT-29 colon carcinoma cells. The thiosemicarbazone and most of the complexes were highly cytotoxic. H2Ac4oClPh and its gallium(III) and tin(IV) complexes did not show any inhibitory activity against thioredoxin reductase (TrxR) and glutathione reductase (GR). The palladium(II), platinum(II) and bismuth(III) complexes inhibited TrxR at micromolar concentrations but not GR. The antimony(III) and gold(III) complexes strongly inhibited TrxR at submicromolar doses with GR inhibition at higher concentrations. The selectivity of these complexes for TrxR suggests metal binding to a selenol residue in the active site of the enzyme. TrxR inhibition is likely a contributing factor to the mode of action of the gold and antimony derivatives. PMID:25058344

  11. Bis(2-acetylpyridine-κ2N,Osilver(I tetrafluoridoborate: a complex with silver in a seesaw coordination geometry

    Michael A. O'Donnell

    2010-12-01

    Full Text Available The reaction of 2-acetylpyridine with silver(I tetrafluoridoborate leads to the discrete title complex, [Ag(C7H7NO2]BF4, in the cation of which the Ag atom is coordinated by two 2-acetylpyridine ligands, each of which is N,O-bidentate, albeit with stronger bonding to the N atoms [Ag—N = 2.2018 (15 and 2.2088 (14 Å; Ag—O = 2.5380 (13 and 2.5454 (13 Å]. The four-coordinate Ag atom has a seesaw coordination geometry with a τ4 index of 0.51. The tetrafluoridoborate anion is disordered over two orientations with 0.568 (10:0.432 (10 occupancies.

  12. Theoretical study of corrosion inhibition of amides and thiosemicarbazones

    An examination of quantum chemical and corrosion inhibition studies were carried out to investigate whether any clear links exist between the results of quantum chemical calculations and the experimental efficiencies of urea (U), thiourea (TU), acetamide (A), thioacetamide (TA), semicarbazide (SC), thiosemicarbazide (TSC), methoxybenzaldehydethiosemicarbazone (MBTSC), 2-acetylpyridine-(4phenyl) thiosemicarbazone (2AP4PTSC), 2-acetylpyridine-(4-methyl) thiosemicarbazone (2AP4MTSC), benzointhiosemicarbazone (BZOTSC) and benzilthiosemicarbazone (BZITSC) being corrosion inhibitors. The quantum chemical calculations have been performed by using DFT, ab-initio molecular orbital and semi-empirical methods for some amides and thiosemicarbozone derivatives being corrosion inhibitors. The highest occupied molecular orbital energy (E HOMO), lowest unoccupied molecular orbital energy (E LUMO), the energy gap between E HOMO and E LUMO (ΔE HOMO-LUMO), dipole moments (μ), charges on the C, O, N, S atoms, the total energies of the molecules and the polarizabilities , the coefficients of the development of the MO over the atomic orbital (AO) corresponding to the between atoms which a new bond is established have been calculated. The results of quantum chemical calculations and experimental efficiencies of inhibitors were subjected to correlation analysis. We have reached the conclusion that the synthesis of better corrosion inhibitors can be achieved by controlling all electronic properties and parameters of a selected group of molecules

  13. Theoretical and infrared investigation of 2-acetylpyridine isolated in solid nitrogen and in neat condensed phases

    Kuş, Nihal

    2016-07-01

    The geometries of the two conformers of 2-acetylpyridine (2AP) were optimized at the DFT/B3LYP/6-311++G(d,p) level of approximation, and their relative energy and interconversion barrier evaluated. Both conformers were found to belong to the Cs symmetry point group, with conformer cis (with the methyl group and the ring nitrogen atom located in the same side of the molecule) being considerably stabilized over the trans form. The cis conformer exhibits stabilizing interactions between the ortho ring hydrogen atom and the carbonyl oxygen, as well as between the methyl out-of-the-plane hydrogen atoms and the ring nitrogen atom. In the less stable trans conformer (ΔE(trans-cis) = 26.3 kJ mol-1) these stabilizing interactions are replaced by repulsive interactions between the oxygen and nitrogen lone electron pairs and between the ring ortho and methyl out-of-the-plane hydrogen atoms. The energy barrier between the two conformers amounts to 30.7 kJ mol-1 in the cis → trans direction (4.4 kJ mol-1 in the reverse direction). In agreement with the theoretical data, in a cryogenic N2 matrix prepared from the room temperature 2AP gas phase, only the most stable cis conformer was observed. The IR spectra of 2AP isolated in solid N2, and those for the low temperature amorphous and crystalline neat solid states of the compound were recorded, and correlations between the spectroscopic data and the strength and nature of the dominant intermolecular interactions in 2AP neat condensed phases were evaluated. The analysis of the experimental vibrational data was supported by theoretical calculation of harmonic and anharmonic frequencies and IR intensities obtained at the DFT/B3LYP/6-311++G(d,p) level of theory.

  14. Interesting copper(ii)-assisted transformations of 2-acetylpyridine and 2-benzoylpyridine.

    Kitos, Alexandros A; Efthymiou, Constantinos G; Manos, Manolis J; Tasiopoulos, Anastasios J; Nastopoulos, Vassilios; Escuer, Albert; Perlepes, Spyros P

    2016-01-21

    The reactions of various copper(ii) sources with 2-acetylpyridine, (py)(me)CO, and 2-benzoylpyridine, (py)(ph)CO, under strongly basic conditions have been studied and novel ligand transformations have been discovered. Reaction of Cu(ClO4)2·6H2O and (py)(me)CO in the presence of NBu4(n)OMe (1 : 1 : 1) in CHCl3 gave a mixture of [Cu2Cl2(HLA)2](ClO4)2 (1) and [Cu2Cl2(LB)2(ClO4)2] (2), where HLA is 3-hydroxy-1,3-di(pyridin-2-yl)-butane-1-one and LB is the zwitterionic-type ligand 3-hydroxy-1-methyl-3-(pyridin-2-yl)-3H-indolizin-4-ium. The ligand HLA is formed through an aldol reaction-type mechanism, while the formation of LB takes place via an intramolecular nucleophilic attack of the remote 2-pyridyl nitrogen atom on the positive carbonyl carbon of HLA, after the transformation of the latter through deprotonation and dehydration. The Cu(II) ions in 1 are bridged by two 2.1111 HLA ligands resulting in a long Cu(II)Cu(II) distance (5.338 Å); the metal ions in 2 are triply bridged by the alkoxide oxygen atoms of the two 2.21 LB ligands and one 2.1100 perchlorato group. The absence of α-hydrogens in (py)(ph)CO leads the reactivity of this ligand in the presence of Cu(II) to different pathways. The Cu(ClO4)2·6H2O/(py)(ph)CO/NBu4(n)OMe reaction mixture in MeOH/H2O (25 : 1 v/v) gave the dinuclear cationic complex [Cu2{(py)(ph)CO}2(LC)2](ClO4)2 (3), where LC(-) is the anion of (methoxy)(phenyl)(pyridin-2-yl)methanol formed in situ via the nucleophilic addition of MeO(-) to the carbonyl carbon of (py)(ph)CO upon Cu(II) coordination. The Cu(II) ions in the cation are doubly bridged by the deprotonated oxygen atoms of the two LC(-) ligands. Replacement of Cu(ClO4)2·6H2O with Cu(NO3)2·3H2O and NBu4(n)OMe with NMe4OH and the decrease of the H2O concentration in the above reaction system yielded the tetranuclear coordination cluster [Cu4(OMe)2(NO3)4{(py)(ph)CO}2(LC)2] (4). The Cu(II) centres in this complex define a parallelogram. Two parallel sides of the

  15. Zinc(II)-Thiosemicarbazone Complexes Are Localized to the Lysosomal Compartment Where They Transmetallate with Copper Ions to Induce Cytotoxicity.

    Stacy, Alexandra E; Palanimuthu, Duraippandi; Bernhardt, Paul V; Kalinowski, Danuta S; Jansson, Patric J; Richardson, Des R

    2016-05-26

    As the di-2-pyridylketone thiosemicarbazone (DpT) and 2-acetylpyridine thiosemicarbazone (ApT) series show potent antitumor activity in vitro and in vivo, we synthesized their fluorescent zinc(II) complexes to assess their intracellular distribution. The Zn(II) complexes generally showed significantly greater cytotoxicity than the thiosemicarbazones alone in several tumor cell-types. Notably, specific structure-activity relationships demonstrated the importance of the di-2-pyridyl pharmacophore in their activity. Confocal fluorescence imaging and live cell microscopy showed that the Zn(II) complex of our lead compound, di-2-pyridylketone 4-cyclohexyl-4-methyl-3-thiosemicarbazone (DpC), which is scheduled to enter clinical trials, was localized to lysosomes. Under lysosomal conditions, the Zn(II) complexes were shown to transmetallate with copper ions, leading to redox-active copper complexes that induced lysosomal membrane permeabilization (LMP) and cytotoxicity. This is the first study to demonstrate direct lysosomal targeting of our novel Zn(II)-thiosemicarbazone complexes that mediate their activity via transmetalation with copper ions and LMP. PMID:27023111

  16. Effect of N(4)-substituent groups on transfer of 2-benzoylpyridine thiosemicarbazone derivates at the water/1,2-dichloroethane interface

    Dependent on the pH of the aqueous phase, the transfer of protonated forms of 2-benzoylpyridine N(4)-phenyl thiosemicarbazone (BPPT) (which has antimicrobial, antifungal and anticytotoxic activities) and 2-benzoylpyridine N(4)-ethyl thiosemicarbazone (BPET) across water/1,2-dichloroethane (1,2-DCE) interface has been studied by cyclic voltammetry. The protonation constants of the ligands (pKa1w and pKa2w) were determined by spectrophotometry. The standard partition coefficients (logPi0) and the standard Gibbs energies of ionic (cationic) species of ligands (ΔGtr,i0,w→o) were calculated from the standard transfer potentials (Δowφi0). The standard Gibbs energies of their transfer (ΔGtr,i0,w→o) and partition coefficients of neutral species (log PN) were determined by shake-flask method. These thermodynamic parameters were evaluated as a quantitative and qualitative measure of the lipophilicities of two compounds. The differences between the partition coefficients of cationic and neutral form of compounds [diff(logPI+-N)] were interpreted by results obtained from voltammetric data. Effect of N(4)-phenyl and ethyl groups for transfer of 2-benzoylpyridine thiosemicarbazone derivatives at macro-liquid/liquid interface was investigated. The antimicrobial activity of BPET was tested against four types of bacteria and found to be active against Staphlylococcus aureus

  17. Synthesis, Cytotoxic and Antimalarial Activities of Benzoyl Thiosemicarbazone Analogs of Isoquinoline and Related Compounds

    Somsak Ruchirawat

    2010-02-01

    Full Text Available Thiosemicarbazone analogs of papaveraldine and related compounds 1–6 were synthesized and evaluated for cytotoxic and antimalarial activities. The cytotoxic activity was tested against HuCCA-1, HepG2, A549 and MOLT-3 human cancer cell lines. Thiosemicarbazones 1–5 displayed cytotoxicity toward all the tested cell lines, while compounds 2–5 selectively showed potent activity against the MOLT-3 cell lines. Significantly, N(4-phenyl-2-benzoylpyridine thiosemicarbazone 4 exhibited the most potent activity against HuCCA-1, HepG2, A549 and MOLT-3 cell lines with IC50 values of 0.03, 4.75, 0.04 and 0.004 µg/mL, respectively. In addition, 2-benzoylpyridine thio-semicarbazones 3 and 4 showed antimalarial activity against Plasmodium falciparum with IC50 of 10-7 to < 10-6 M. The study demonstrates the quite promising activity of analog 4 as a lead molecule for further development.

  18. Benzaldehyde thiosemicarbazone

    Xiu-Ping Ju

    2008-12-01

    Full Text Available The title compound, C8H9N3S, contains two molecules in the asymmetric unit. One molecule is close to being planar (r.m.s. deviation from the mean plane = 0.06 Å for the non-H atoms, while the other exhibits a dihedral angle of 21.7 (1° between the benzene ring and the mean plane of the thiosemicarbazone unit. Intermolecular N—H...S hydrogen bonds link the molecules into layers parallel to the (010 plane.

  19. Bismuth(III) complexes with 2-acetylpyridine- and 2-benzoylpyridine-derived hydrazones: Antimicrobial and cytotoxic activities and effects on the clonogenic survival of human solid tumor cells.

    Ferreira, Isabella P; Piló, Elisa D L; Recio-Despaigne, Angel A; Da Silva, Jeferson G; Ramos, Jonas P; Marques, Lucas B; Prazeres, Pedro H D M; Takahashi, Jacqueline A; Souza-Fagundes, Elaine M; Rocha, Willian; Beraldo, Heloisa

    2016-07-01

    Complexes [Bi(2AcPh)Cl2]·0.5H2O (1), [Bi(2AcpClPh)Cl2] (2), [Bi(2AcpNO2Ph)Cl2] (3), [Bi(2AcpOHPh)Cl2]·2H2O (4), [Bi(H2BzPh)Cl3]·2H2O (5), [Bi(H2BzpClPh)Cl3] (6), [Bi(2BzpNO2Ph)Cl2]·2H2O (7) and [Bi(H2BzpOHPh)Cl3]·2H2O (8) were obtained with 2-acetylpyridine phenylhydrazone (H2AcPh), its -para-chloro-phenyl- (H2AcpClPh), -para-nitro-phenyl (H2AcpNO2Ph) and -para-hydroxy-phenyl (H2AcpOHPh) derivatives, as well as with the 2-benzoylpyridine phenylhydrazone analogues (H2BzPh, H2BzpClPh, H2BzpNO2Ph, H2BzpOHPh). Upon coordination to bismuth(III) antibacterial activity against Gram-positive and Gram-negative bacterial strains significantly improved except for complex (4). The cytotoxic effects of the compounds under study were evaluated on HL-60, Jurkat and THP-1 leukemia, and on MCF-7 and HCT-116 solid tumor cells, as well as on non-malignant Vero cells. In general, 2-acetylpyridine-derived hydrazones proved to be more potent and more selective as cytotoxic agents than the corresponding 2-benzoylpyridine-derived counterparts. Exposure of HCT-116 cells to H2AcpClPh, H2AcpNO2Ph and complex (3) led to 99% decrease of the clonogenic survival. The IC50 values of these compounds were three-fold smaller when cells were cultured in soft-agar (3D) than when cells were cultured in monolayer (2D), suggesting that they constitute interesting scaffolds, which should be considered in further studies aiming to develop new drug candidates for the treatment of colon cancer. PMID:27209169

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

    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.

  1. Manganese(II) complexes with thiosemicarbazones as potential anti-Mycobacterium tuberculosis agents.

    Oliveira, Carolina G; da S Maia, Pedro Ivo; Souza, Paula C; Pavan, Fernando R; Leite, Clarice Q F; Viana, Rommel B; Batista, Alzir A; Nascimento, Otaciro R; Deflon, Victor M

    2014-03-01

    Through a systematic variation on the structure of a series of manganese complexes derived from 2-acetylpyridine-N(4)-R-thiosemicarbazones (Hatc-R), structural features have been investigated with the aim of obtaining complexes with potent anti-Mycobacterium tuberculosis activity. The analytical methods used for characterization included FTIR, EPR, UV-visible, elemental analysis, cyclic voltammetry, magnetic susceptibility measurement and single crystal X-ray diffractometry. Density functional theory (DFT) calculations were performed in order to evaluate the contribution of the thiosemicarbazonate ligands on the charge distribution of the complexes by changing the peripheral groups as well as to verify the Mn-donor atoms bond dissociation predisposition. The results obtained are consistent with the monoanionic N,N,S-tridentate coordination of the thiosemicarbazone ligands, resulting in octahedral complexes of the type [Mn(atc-R)2], paramagnetic in the extension of 5 unpaired electrons, whose EPR spectra are consistent for manganese(II). The electrochemical analyses show two nearly reversible processes, which are influenced by the peripheral substituent groups at the N4 position of the atc-R(1-) ligands. The minimal inhibitory concentration (MIC) of these compounds against M. tuberculosis as well as their in vitro cytotoxicity on VERO and J774A.1 cells (IC50) was determined in order to find their selectivity index (SI) (SI=IC50/MIC). The results evidenced that the compounds described here can be considered as promising anti-M. tuberculosis agents, with SI values comparable or better than some commercial drugs available for the tuberculosis treatment. PMID:24188534

  2. Spectral characterization of iron(III) complexes of 2-benzoylpyridine N(4)-substituted thiosemicarbazones

    Joseph, Marthakutty; Sreekanth, Anandaram; Suni, V.; Kurup, M. R. Prathapachandra

    2006-06-01

    Three iron(III) complexes (1-3) of 2-benzoylpyridine N(4)-phenyl thiosemicarbazone (HL 1) and one iron(III) complex (4) of 2-benzoylpyridine N(4)-cyclohexyl thiosemicarbazone (HL 2) were synthesized and characterized by means of different physicochemical techniques viz., molar conductivity measurements, magnetic susceptibility studies and electronic, infrared and EPR spectral studies. The analytical data and the molar conductance measurements of the complexes reveal that two molecules of the ligand and the anion are coordinated to the metal atom in all the four complexes. The magnetic moments of the complexes suggest that they are of low spin. From the infrared spectra of the ligands and the complexes it is confirmed that the ligands coordinate to iron(III) as an anion coordinating via the azomethine nitrogen, pyridyl nitrogen, and the thiolate sulphur. The EPR spectra of the complexes in the polycrystalline state at 298 and 110 K and in DMF solution at 110 K were recorded and all the spectra show three g values indicating that these complexes have rhombic distortion. All the iron(III) complexes in DMF solution at 110 K have similar anisotropic spectra with almost the same gav values, indicating that the bonding in all the complexes is similar and is unaffected by the coordination of the anion.

  3. Separation and determination of chromium (iii) chromium (vi), gold (iii) and arsenic (v) by capillary zone electrophoresis using 2-acetylpyridine-4-phenylthiosemicarbazone as complexing reagent

    Capillary zone electrophoretic procedure has been developed for the speciation of Cr (III) and Cr (VI) along with separation from Au (III) and As (V) as chelate compounds of 2-acetylpyridine-4-phenylthiosemicarbazone (APPT). APPT reacts with Cr (III), Cr (VI), Au (III) and As (V) to form water-methanol soluble chelates which absorb maximally within 360 - 418 nm with molar absorptivity of 3.2 * 103 to 1.2*104 L mol-1cm-1. Off line pre-capillary complexes of the cations prepared were introduced onto uncoated fused silica capillary of 54 cm effective length with 75 micro m id by auto-sampler and separated with background electrolyte (BGE) system of oxalate buffer at pH-4 at an applied voltage of +15 kV. Photodiode array detection was carried out at 241 nm. Linear calibrations were obtained within 1-80 micro gmL-1 for all the cations. The separation and quantitation was repeatable in terms of migration time and peak height with relative standard deviation (RSD) within 2% (n=4). The limit of detection (LOD) measured were 0.125 micro gmL-1, 1.0 micro gmL-1, 0.2 micro gmL-1 and 0.1 respectively for Au(III), As(V), Cr (III) and Cr(VI). The limits of quantitation (LOQ) were in the range of 0.375- 3.0 micro gmL-1. The method was applied for the determination of Cr (III) from tap water, Cr (VI) from industrial effluents and Au (III) and As (V) from pore water of coal mines with RSD within 4%. The results of analysis were supported by standard addition method and rechecked by atomic absorption spectrometry (AAS). (author)

  4. Thiosemicarbazone complexes of technetium

    One aproach to the design of new sup(99m)Tc-radiopharmaceuticals consists in the preparation of bifunctional radio-pharmaceuticals [1]. In this approach, a bifunctional molecule is synthesized which possesses a chelating functional group (capable of forming a stable complex with sup(99m)Tc) attached to a second functional group which is expected to have a useful biological distribution. Thiosemicarbazones are compounds that possess great chelating capacity [2] and are easily obtainable by condensation of the theosemicarbazide (H2N-NH-CS-NH2) or substituted thiosemicarbazide with the carbonyl groups of aldehydes or ketones. Consequently transformation of molecules of biological interest that the carbonyl group possess in thiosemicarbazones is simple and these modified molecules could act a bifunctional radiopharmaceuticals. For this reason a series of thiosemicarbazone complexes of 99Tc was prepared. This is the first report on technetium complexes with thiosemicarbazones. (orig.)

  5. Thiosemicarbazone complexes of technetium

    Grases, F.; Genestar, C.

    1985-01-01

    One aproach to the design of new sup(99m)Tc-radiopharmaceuticals consists in the preparation of bifunctional radio-pharmaceuticals (1). In this approach, a bifunctional molecule is synthesized which possesses a chelating functional group (capable of forming a stable complex with sup(99m)Tc) attached to a second functional group which is expected to have a useful biological distribution. Thiosemicarbazones are compounds that possess great chelating capacity (2) and are easily obtainable by condensation of the theosemicarbazide (H/sub 2/N-NH-CS-NH/sub 2/) or substituted thiosemicarbazide with the carbonyl groups of aldehydes or ketones. Consequently transformation of molecules of biological interest that the carbonyl group possess in thiosemicarbazones is simple and these modified molecules could act as bifunctional radiopharmaceuticals. For this reason a series of thiosemicarbazone complexes of /sup 99/Tc was prepared. This is the first report on technetium complexes with thiosemicarbazones.

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

    A 119Sn Moessbauer 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 Moessbauer 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 Moessbauer 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.

  7. 3-Methoxybenzaldehyde thiosemicarbazone

    Jian Zhang

    2009-04-01

    Full Text Available The title compound, C9H11N3OS, was prepared by the reaction of 3-methoxybenzaldehyde and thiosemicarbazide. The benzylidene ring and the thiosemicarbazone fragment are slightly twisted, making a dihedral angle of 14.1 (1°. A weak intramolecular N—H...N hydrogen bond may influence the conformation of the molecule. Intermolecular N—H...S hydrogen bonds build up a three-dimensional network.

  8. Pyridine-2-carbaldehyde thiosemicarbazone

    Sheng-Xiang Yang; Kun Jiang; Xiang Zhang; Li-Hua Song

    2009-01-01

    The asymmetric unit of the title compound, C7H8N4S, contains two independent molecules with slightly different conformations; the dihedral angles between the pyridine ring and mean plane of the thiosemicarbazone unit in the two molecules are 2.88 (5) and 6.30 (5)°. Intermolecular N—H...N and N—H...S hydrogen bonds link the molecules into layers parallel to the ab plane.

  9. 3-Methoxybenzaldehyde thiosemicarbazone

    Jian Zhang; Lin-ping Wu; Ling-hua Zhuang; Guo-wei Wang

    2009-01-01

    The title compound, C9H11N3OS, was prepared by the reaction of 3-methoxybenzaldehyde and thiosemicarbazide. The benzylidene ring and the thiosemicarbazone fragment are slightly twisted, making a dihedral angle of 14.1 (1)°. A weak intramolecular N—H...N hydrogen bond may influence the conformation of the molecule. Intermolecular N—H...S hydrogen bonds build up a three-dimensional network.

  10. Pyridine-2-carbaldehyde thiosemicarbazone

    Sheng-Xiang Yang

    2009-02-01

    Full Text Available The asymmetric unit of the title compound, C7H8N4S, contains two independent molecules with slightly different conformations; the dihedral angles between the pyridine ring and mean plane of the thiosemicarbazone unit in the two molecules are 2.88 (5 and 6.30 (5°. Intermolecular N—H...N and N—H...S hydrogen bonds link the molecules into layers parallel to the ab plane.

  11. (E-4-Octyloxybenzaldehyde thiosemicarbazone

    M. A. A. A. A. Islam

    2010-01-01

    Full Text Available In the title compound, C16H25N3OS, the thiosemicarbazone group adopts an E configuration with respect to the C=N bond and is almost coplanar with the benzene ring, forming a dihedral angle of 9.3 (1°. In the crystal packing, the molecules lie along the a axis in an antiparallel arrangement and are held in place by van der Waals interactions. As a consequence, there is relatively low anisotropic thermal motion in the terminal atoms of the n-octyl chain.

  12. Preparation of 35S labelled thiosemicarbazone

    A 35S labelled thiosemicarbazone is prepared, on a millimole scale by reacting labelled thiocyanate with hydrazine sulfate in ethanolic medium. The hydrazine thiocyanate so formed is then condensed with aldehyde to form the thiosemicarbazone

  13. A {sup 119}Sn Moessbauer Study of Tin(IV) Complexes of 2- and 4-Benzoylpyridine Thiosemicarbazone and 4-Benzoylpyridine Semicarbazone

    Perez-Rebolledo, Anayive [Universidade Federal de Minas Gerais, Departamento de Quimica (Brazil); Ardisson, Jose D., E-mail: jdr@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear, Laboratorio de Fisica Aplicada (LFA/CDTN) (Brazil); Lima, Geraldo M. de [Universidade Federal de Minas Gerais, Departamento de Quimica (Brazil); Macedo, Waldemar A. A. [Centro de Desenvolvimento da Tecnologia Nuclear, Laboratorio de Fisica Aplicada (LFA/CDTN) (Brazil); Beraldo, Heloisa, E-mail: hberaldo@ufmg.br [Universidade Federal de Minas Gerais, Departamento de Quimica (Brazil)

    2005-06-15

    A {sup 119}Sn Moessbauer 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)Cl{sub 3}] (1), [Sn(2Bz4DH)PhCl{sub 2}] (2), [Sn(2Bz4M)Cl{sub 3}] (3), [H{sub 2}2Bz4M]{sub 2}[Ph{sub 2}SnCl{sub 4}] (4), [Sn(2Bz4Ph)PhCl{sub 2}] (5), [Sn(2Bz4Ph)Ph{sub 2}Cl] (6), in which H2Bz4R stands for the neutral ligand and 2Bz4R stands for the anionic thiosemicarbazone. In addition, {sup 119}Sn Moessbauer studies of the tin(IV) complexes [Sn(H4Bz4DH){sub 2}Cl{sub 4}H{sub 2}O] (7), [Sn(H4BzPS){sub 2}Cl{sub 4}H{sub 2}O] (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 sp{sup 3} hybridization in the tin salts to sp{sup 3}d{sup 2} in the octahedral or sp{sup 3}d{sup 3} in the heptahedral complexes. The Moessbauer 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.

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

    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.

  15. Syntheses, structural and spectral studies of six-coordinate, [Ph 2SnCl(acpm)], and seven-coordinate, [ nBu 2Sn(dapm)], diorganotin(IV) complexes with N, N, S-tridentate and S, N, N, N, S-pentadentate N4-heterocyclic thiosemicarbazones

    de Sousa, Gerimário F.; Manso, Luís Carlos C.; Lang, Ernesto S.; Gatto, Claudia C.; Mahieu, Bernard

    2007-01-01

    The reaction of the N, N, S-tridentate ligand 2-acetylpyridine ( N4-morpholyl thiosemicarbazones), Hacpm, with Ph 2SnCl 2 leads to the formation of the six-coordinate complex [Ph 2SnCl(acpm)] ( 1), whereas the reaction of the S, N, N, N, S-pentadentate ligand 2,6-diacetylpyridine bis( N4-morpholyl thiosemicarbazone), H 2dapm, with nBu 2SnCl 2 leads to the formation of the seven-coordinate complex [ nBu 2Sn(dapm)] ( 2). Both compounds were studied by microanalyses, IR, NMR ( 1H, 13C, 119Sn) and Mössbauer spectroscopy to investigate their structural properties. The organotin(IV) complexes were also studied by single crystal X-ray diffraction and the structure determination revealed that the phenyl derivative crystallizes in the triclinic space group (P1¯) as discrete neutral molecules, with the tin(IV) ion in a distorted octahedral geometry with the acpm 1- ligand in a meridional configuration and the phenyl groups in trans positions. X-ray analysis shows that the n-butyl complex crystallizes in the monoclinic space group ( P2 1/ c) as discrete neutral complexes, with the tin(IV) ion in a distorted pentagonal bipyramidal geometry. A correlation between Mössbauer and X-ray data based on the point-charge model is discussed.

  16. Metal complexes with paramagnetic thiosemicarbazone

    The complexes of Ni(2), Fe(2), Zn(2), Cd(2), Pd(2) and Pt(2) with the stable nitroxyl radical of thiosemicarbazone 4-formyl- 2, 2, 5, 5-tetramethyl-3-imidazoline-1-oxyl of the composition ML2 are synthesized. In the basis of the data of physical methods (IR, EPR, electron spectroscopy) a conclusion is made on the way of the ligand coordination. The study of the magnetic properties of the complexes has shown that in the compounds prepared a weak exchange interaction between unpaired electrons of paramagnetic centres takes place

  17. Antifungal activities of thiosemicarbazones and semicarbazones against mycotoxigenic fungi

    Rojane de Oliveira Paiva

    2014-12-01

    Full Text Available Mycotoxigenic fungi can compromise the quality of food, exposing human and animal health at risk. The antifungal activity of eight thiosemicarbazones (1-8 and nine semicarbazones (9-17 was evaluated against Aspergillus flavus, A. nomius, A. ochraceus, A. parasiticus and Fusarium verticillioides. Thiosemicarbazones had MIC values of 125-500 µg/ml. The thiosemicarbazones 1 and 2 exerted fungistatic activity against Aspergillus spp., and thiosemicarbazone 2 exerted fungicidal activity against F. verticillioides. Compound 2 showed an iron chelating effect of 63%. The ergosterol content of A. parasiticus had a decrease of 28 and 71% for the 31.2 and 62.5 µg/ml concentrations of thiosemicarbazone 2 compared to the control. The obtained results of antifungal activity revealed that thiosemicarbazone class was more active when compared to semicarbazone class and, the thiosemicarbazone 2 was the most active compound, specially, against Aspergillus spp.

  18. Biodistribution of /sup 59/Fe-thiosemicarbazones

    Hanson, R.N.; Davis, M.A.

    1982-01-01

    The /sup 59/Fe-iron(II) chelates of 2-formylpyridine thiosemicarbazone (I), 5-dimethylamino-2-formylpyridine thiosemicarbazone (II), and 5-hydroxy-2-formylpyridine thiosemicarbazone (III) were prepared and their biodistribution determined in normal rats. Early accumulation of these complexes occurred in the liver, muscle and pelt with lesser amounts in the blood, kidneys and other organs. The tissue levels decreased with a 1 to 2-h half-life with the exception of the liver and intestines. The liver level tended to remain constant over the 2-h period. Accumulation in the gut resulting from hepatobiliary excretion increased over the first 60 min and then leveled off. In rats bearing a subcutaneous glioblastoma the uptake of compound I increased during the first 24 h after administration, and tumor to normal tissue ratios of 2 to 3.3 were obtained.

  19. 3-Hydroxy-4-methoxybenzaldehyde thiosemicarbazone hemihydrate

    S. M. Dharmaprakash; Patil, P. S.; E. Deepak D'Silva; Reza Kia; Hoong-Kun Fun

    2008-01-01

    The asymmetric unit of the title compound, C9H11N3O2S·0.5H2O, comprises two crystallograpically independent thiosemicarbazone molecules (A and B) and a water molecule of crystallization. In each of the thiosemicarbazone molecules, intramolecular O—H...O and N—H...N hydrogen bonds form five-membered rings, producing S(5) ring motifs. Intermolecular O—H...S and N—H...O interactions between molecule B and the water molecule form a six-membered ring, producing an R22(...

  20. Antiretroviral activity of thiosemicarbazone metal complexes.

    Pelosi, Giorgio; Bisceglie, Franco; Bignami, Fabio; Ronzi, Paola; Schiavone, Pasqualina; Re, Maria Carla; Casoli, Claudio; Pilotti, Elisabetta

    2010-12-23

    Thiosemicarbazones display a wide antimicrobial activity by targeting bacteria, fungi, and viruses. Here, we report our studies on the antiviral activity of two thiosemicarbazone metal complexes, [bis(citronellalthiosemicarbazonato)nickel(II)] and [aqua(pyridoxalthiosemicarbazonato)copper(II)] chloride monohydrate, against the retroviruses HIV-1 and HTLV-1/-2. Both compounds exhibit antiviral properties against HIV but not against HTLVs . In particular, the copper complex shows the most potent anti-HIV activity by acting at the post-entry steps of the viral cycle. PMID:21121632

  1. ANTIMICROBIAL ACTIVITY OF DIFFERENT THIOSEMICARBAZONE COMPOUNDS AGAINST MICROBIAL PATHOGENS

    Negi Parul; Nandy Subhangkar; Mahato Arun

    2012-01-01

    Thiosemicarbazone belongs to a large group of thiourea derivatives, whose biological activities are a function of parent aldehyde or ketone moiety. They have been evaluated over the last 50 year as antiviral, antibacterial, antifungal, antimalarial, anticancer, leprosy, rheumatism, trypanosomiasis and coccidiodis. Thiosemicarbazones were prepared by simple process in which N4-thiosemicarbazone moiety was replaced by aliphatic, arylic and cyclic amines. Present study reported the anti-microbia...

  2. Nickel Complexes of Thiosemicarbazone Derivatives of Lawsone

    Sanjay Gaikwad

    2013-01-01

    Thiosemicarbazone derivative at 1 position of the Lawsone ( 2-hydroxy-1,4-naphthalenedione ) i.e. 1-TSCND is an important derivative, Which possesses a powerful chelating ability, appreciable analytical utility and significant biological activity[1]. Its Nickel (II) complex is newly reported here

  3. Nickel Complexes of Thiosemicarbazone Derivatives of Lawsone

    Sanjay Gaikwad

    2013-06-01

    Full Text Available Thiosemicarbazone derivative at 1 position of the Lawsone ( 2-hydroxy-1,4-naphthalenedione i.e. 1-TSCND is an important derivative, Which possesses a powerful chelating ability, appreciable analytical utility and significant biological activity[1]. Its Nickel (II complex is newly reported here

  4. ANTIMICROBIAL ACTIVITY OF DIFFERENT THIOSEMICARBAZONE COMPOUNDS AGAINST MICROBIAL PATHOGENS

    Negi Parul

    2012-05-01

    Full Text Available Thiosemicarbazone belongs to a large group of thiourea derivatives, whose biological activities are a function of parent aldehyde or ketone moiety. They have been evaluated over the last 50 year as antiviral, antibacterial, antifungal, antimalarial, anticancer, leprosy, rheumatism, trypanosomiasis and coccidiodis. Thiosemicarbazones were prepared by simple process in which N4-thiosemicarbazone moiety was replaced by aliphatic, arylic and cyclic amines. Present study reported the anti-microbial activity of different thiosemicarbazone compounds against certain bacterial and fungal pathogens viz. Bacillus cereus, Staphylococcus epidermis, Moraxella cattarhalis, Staph. Saprophyticus, Candida albicans and Aspergillus flavans.

  5. SYNTHESIS AND BIOEVALUATION OF KETOCONAZOLE THIOSEMICARBAZONE ANALOGUES

    Y. Murti

    2011-01-01

    Ketoconazole (KTZ) is a synthetic antifungal drug used to prevent and treat fungal infections, especially in immunocompromised patients such as those with AIDS. Resistance to ketoconazole has been observed in a number of clinical fungal isolates, including C. albicans. Thus new effective agents with less toxicity against fungal infection are urgently required. With this view, ketoconazole thiosemicarbazone analogues (Compounds 1-10) were synthesized wherein condensation of different thiosemic...

  6. Metal chelates of 2-acetylbenzimidazole thiosemicarbazones

    Earlier unknown complexes of ML' and ML2 compositions were prepared on the basis of thiosemicarbazones of 2-acetylbenzimidazole (L'H2) and 2-acetyl-1-methylbenzimidazole (LH) and metal (M=Cu2+, VO2+, Co2+, Ni2+) acetates in ethanol medium. Data of IR and ESR spectra and magnetochemical measurements, as well as correlation of experimental and calculated values of the polar magnetic susceptibility in 80-300K range enabled to assign polymeric structure to complexes of ML' composition and monomeric structure - to complexes of ML2 composition

  7. Trypanotoxic activity of thiosemicarbazone iron chelators

    Ellis, Samuel; Sexton, Darren; Steverding, Dietmar

    2015-01-01

    Only a few drugs are available for treating sleeping sickness and nagana disease; parasitic infections caused by protozoans of the genus Trypanosoma in sub-Saharan Africa. There is an urgent need for the development of new medicines for chemotherapy of these devastating diseases. In this study, three newly designed thiosemicarbazone iron chelators, TSC24, Dp44mT and 3-AP, were tested for in vitro activity against bloodstream forms of T. brucei and human leukaemia HL-60 cells. In addition to t...

  8. 2-Hydroxyimino-1-phenylethanone thiosemicarbazone monohydrate

    Tuncer Hökelek; Ertan Şahin; knur Babahan; Nursabah Sarıkavaklı

    2008-01-01

    In the title thiosemicarbazone derivative, C9H10N4OS·H2O, intramolecular N—H...N hydrogen bonds result in the formation of two nearly coplanar five- and six-membered rings, which are also almost coplanar with the adjacent phenyl ring. The oxime group has an E configuration and is involved in intermolecular O—H...O hydrogen bonding as a donor. In the crystal structure, intramolecular O—H...S and N—H...N and intermolecular O—H...O and N—H...S hydrogen bo...

  9. Management of 3-aminopyridine-2-carboxaldehyde thiosemicarbazone-induced methemoglobinemia

    Kunos, Charles A; Radivoyevitch, Tomas; Ingalls, Stephen T; Hoppel, Charles L

    2012-01-01

    The anticancer agent 3-aminopyridine-2-carboxaldehyde thiosemicarbazone is a ribonucleotide reductase inhibitor. It inactivates ribonucleotide reductase by disrupting an iron-stabilized radical in ribonucleotide reductase's small subunits, M2 and M2b (p53R2). Unfortunately, 3-aminopyridine-2-carboxaldehyde thiosemicarbazone also alters iron II (Fe2+) in hemoglobin. This creates Fe3+ methemoglobin that does not deliver oxygen. Fe2+ in hemoglobin normally auto-oxidizes to inactive Fe3+ methemoglobin at a rate of nearly 3% per day and this is counterbalanced by a reductase system that normally limits methemoglobin concentrations to less than 1% of hemoglobin. This balance may be perturbed by symptomatic toxicity levels during 3-aminopyridine-2-carboxaldehyde thiosemicarbazone therapy. Indications of 3-aminopyridine-2-carboxaldehyde thiosemicarbazone sequelae attributable to methemoglobinemia include resting dyspnea, headaches and altered cognition. Management of methemoglobinemia includes supplemental oxygen, ascorbate and, most importantly, intravenously administered methylene blue as a therapeutic antidote. PMID:22335579

  10. Study of complexes of isonitrosoacetophenone thiosemicarbazone (Preprint No. CT-32)

    Uranyl complexes of isonitrosoacetophenone thiosemicarbazone (INAPT) have been synthesized and characterized with the aid of analytical, conductance and spectral (IR, electronic, 1H NMR and TG) studies. (author). 6 refs

  11. Ferromagnetism in Cu 3-thiosemicarbazone- 2,3-dioxoindole complexes

    Zentková, M.; Kováč, J.; Zentko, A.; Košturiak, A.

    1991-12-01

    We report evidence for ferromagnetic ordering in Cu-chelates of 3-thiosemicarbazone-2,3-dioxoindole (isatine). It has been found that the Curie temperature is 16.8 K and is independent of the Cu content.

  12. Management of 3-aminopyridine-2-carboxaldehyde thiosemicarbazone-induced methemoglobinemia

    Kunos, Charles A.; Radivoyevitch, Tomas; Ingalls, Stephen T.; Hoppel, Charles L.

    2012-01-01

    The anticancer agent 3-aminopyridine-2-carboxaldehyde thiosemicarbazone is a ribonucleotide reductase inhibitor. It inactivates ribonucleotide reductase by disrupting an iron-stabilized radical in ribonucleotide reductase's small subunits, M2 and M2b (p53R2). Unfortunately, 3-aminopyridine-2-carboxaldehyde thiosemicarbazone also alters iron II (Fe2+) in hemoglobin. This creates Fe3+ methemoglobin that does not deliver oxygen. Fe2+ in hemoglobin normally auto-oxidizes to inactive Fe3+ methemog...

  13. Synthesis, characterization and biological activity of uranyl thiosemicarbazone complexes

    A new thiosemicarbazone namely phenacyl thioacetic acid thiosemicarbazone was synthesized and its UO22+ complexes were prepared. The synthesized ligand and complexes were characterized by elemental analyses, spectral (IR, 1H NMR and Mass) studies. In all complexes the ligand coordinates through carboxylic oxygen, azomethine nitrogen and thiolate sulfur. Antimicrobial screening of the free ligand and its complexes showed that, the free ligand and metal complexes possess antimicrobial activities towards two types of bacteria and two types of fungi. (author)

  14. Synthesis, structure and electrochemical properties of some thiosemicarbazone complexes of ruthenium

    Datta, S.; Drew, Michael G B; Bhattacharya, S.

    2011-01-01

    Reaction of salicylaldehyde thiosemicarbazone (L-1), 2-hydroxyacetophenone thiosemicarbazone (L-2) and 2-hydroxynapthaldehyde thiosemicarbazone (L-3) with [Ru(dmso)(4)Cl-2] affords a family of three dimeric complexes (1), (2) and (3) respectively. Crystal structure of the complex (3) has been determined. In these complexes, each monomeric unit consists of one ruthenium center and two thiosemicarbazone ligands, one of which is coordinated to ruthenium as O,N,S-donor and the other as N,S-donor ...

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

    Georges C. Accrombessi; Jacques Poupaert; Raymond H. Fatondji; Salomé D. S. Kpoviessi; Gbaguidi, Fernand A.; Bienvenu Glinma

    2011-01-01

    The structure of four synthesized thiosemicarbazones, substituted or not, of benzophenone has been confirmed by spectrometrical analysis IR, NMR 1H and 13C. Their anti-trypanosomal activities were evaluated on Trypanosoma brucei brucei. Among these compounds, benzophenone 4 phenyl-3-thiosemicarbazone 4 has the highest activity with the half-inhibitory concentration (IC50) = 8.48 micromolar (µM). Benzophenone 4-methyl-3-thiosemicarbazone 3 and benzophenone thiosemicarbazone 1 showed moderate a...

  16. Coordination behavior of ligand based on NNS and NNO donors with ruthenium(III) complexes and their catalytic and DNA interaction studies

    Manikandan, R.; Viswnathamurthi, P.

    2012-11-01

    Reactions of 2-acetylpyridine-thiosemicarbazone HL1, 2-acetylpyridine-4-methyl-thiosemicarbazone HL2, 2-acetylpyridine-4-phenyl-thiosemicarbazone HL3 and 2-acetylpyridine-semicarbazone HL4 with ruthenium(III) precursor complexes were studied and the products were characterized by analytical and spectral (FT-IR, electronic, EPR and EI-MS) methods. The ligands coordinated with the ruthenium(III) ion via pyridine nitrogen, azomethine nitrogen and thiolate sulfur/enolate oxygen. An octahedral geometry has been proposed for all the complexes based on the studies. All the complexes are redox active and display an irreversible and quasireversible metal centered redox processes. Further, the catalytic activity of the new complexes has been investigated for the transfer hydrogenation of ketones in the presence of isopropanol/KOH and the Kumada-Corriu coupling of aryl halides with aryl Grignard reagents. The DNA cleavage efficiency of new complexes has also been tested.

  17. 3-Hydroxy-4-methoxybenzaldehyde thiosemicarbazone hemihydrate

    S. M. Dharmaprakash

    2008-12-01

    Full Text Available The asymmetric unit of the title compound, C9H11N3O2S·0.5H2O, comprises two crystallograpically independent thiosemicarbazone molecules (A and B and a water molecule of crystallization. In each of the thiosemicarbazone molecules, intramolecular O—H...O and N—H...N hydrogen bonds form five-membered rings, producing S(5 ring motifs. Intermolecular O—H...S and N—H...O interactions between molecule B and the water molecule form a six-membered ring, producing an R22(6 ring motif. Intermolecular N—H...S hydrogen bonds form dimers involving pairs of both A and B molecules, which form R22(8 ring motifs. The angles between the aromatic ring and thiourea unit in the two molecules are 0.80 (6 and 3.28 (5°, which proves that each molecule is fairly planar. The crystal structure is stabilized by intermolecular O—H...S (×2, O—H...O, N—H...S (×2 and N—H...O (×2 hydrogen bonds and C—H...O (×2 contacts to form a three-dimensional network.

  18. SYNTHESIS AND BIOEVALUATION OF KETOCONAZOLE THIOSEMICARBAZONE ANALOGUES

    Y. Murti

    2011-12-01

    Full Text Available Ketoconazole (KTZ is a synthetic antifungal drug used to prevent and treat fungal infections, especially in immunocompromised patients such as those with AIDS. Resistance to ketoconazole has been observed in a number of clinical fungal isolates, including C. albicans. Thus new effective agents with less toxicity against fungal infection are urgently required. With this view, ketoconazole thiosemicarbazone analogues (Compounds 1-10 were synthesized wherein condensation of different thiosemicarbazides substituted by different cyclic and aromatic amines with the KTZ was done. Investigation of in-vitro antifungal activity of compounds was done by broth microdilution assay method against five pathogenic fungi Aspergillus niger, Candida albicans, Candida krusei, Candida glabrata and Candida tropicalis. Ketoconazole was used as reference for inhibitory activity against fungi. All the compounds were found potent antifungal agents, while compounds 8, 9 and 10 exhibited excellent in-vitro antifungal activity showing importance of halogenated compounds.

  19. 2-Hydroxyimino-1-phenylethanone thiosemicarbazone monohydrate

    Tuncer Hökelek

    2008-03-01

    Full Text Available In the title thiosemicarbazone derivative, C9H10N4OS·H2O, intramolecular N—H...N hydrogen bonds result in the formation of two nearly coplanar five- and six-membered rings, which are also almost coplanar with the adjacent phenyl ring. The oxime group has an E configuration and is involved in intermolecular O—H...O hydrogen bonding as a donor. In the crystal structure, intramolecular O—H...S and N—H...N and intermolecular O—H...O and N—H...S hydrogen bonds generate edge-fused R22(8 and R41(11 ring motifs. The hydrogen-bonded motifs are linked to each other to form a three-dimensional supramolecular network.

  20. Trypanotoxic activity of thiosemicarbazone iron chelators.

    Ellis, Samuel; Sexton, Darren W; Steverding, Dietmar

    2015-03-01

    Only a few drugs are available for treating sleeping sickness and nagana disease; parasitic infections caused by protozoans of the genus Trypanosoma in sub-Saharan Africa. There is an urgent need for the development of new medicines for chemotherapy of these devastating diseases. In this study, three newly designed thiosemicarbazone iron chelators, TSC24, Dp44mT and 3-AP, were tested for in vitro activity against bloodstream forms of Trypanosoma brucei and human leukaemia HL-60 cells. In addition to their iron chelating properties, TSC24 and Dp44mT inhibit topoisomerase IIα while 3-AP inactivates ribonucleotide reductase. All three compounds exhibited anti-trypanosomal activity, with minimum inhibitory concentration (MIC) values ranging between 1 and 100 µM and 50% growth inhibition (GI50) values of around 250 nM. Although the compounds did not kill HL-60 cells (MIC values >100 µM), TSC24 and Dp44mT displayed considerable cytotoxicity based on their GI50 values. Iron supplementation partly reversed the trypanotoxic and cytotoxic activity of TSC24 and Dp44mT but not of 3-AP. This finding suggests possible synergy between the iron chelating and topoisomerase IIα inhibiting activity of the compounds. However, further investigation using separate agents, the iron chelator deferoxamine and the topoisomerase II inhibitor epirubicin, did not support any synergy for the interaction of iron chelation and topoisomerase II inhibition. Furthermore, TSC24 was shown to induce DNA degradation in bloodstream forms of T. brucei indicating that the mechanism of trypanotoxic activity of the compound is topoisomerase II independent. In conclusion, the data support further investigation of thiosemicarbazone iron chelators with dual activity as lead compounds for anti-trypanosomal drug development. PMID:25595343

  1. Methemoglobin formation by triapine, di-2-pyridylketone-4,4-dimethyl-3-thiosemicarbazone (Dp44mT), and other anticancer thiosemicarbazones: identification of novel thiosemicarbazones and therapeutics that prevent this effect.

    Quach, Patricia; Gutierrez, Elaine; Basha, Maram Talal; Kalinowski, Danuta S; Sharpe, Philip C; Lovejoy, David B; Bernhardt, Paul V; Jansson, Patric J; Richardson, Des R

    2012-07-01

    Thiosemicarbazones are a group of compounds that have received comprehensive investigation as anticancer agents. The antitumor activity of the thiosemicarbazone, 3-amino-2-pyridinecarboxaldehyde thiosemicarbazone (3-AP; triapine), has been extensively assessed in more than 20 phase I and II clinical trials. These studies have demonstrated that 3-AP induces methemoglobin (metHb) formation and hypoxia in patients, limiting its usefulness. Considering this problem, we assessed the mechanism of metHb formation by 3-AP compared with that of more recently developed thiosemicarbazones, including di-2-pyridylketone-4,4-dimethyl-3-thiosemicarbazone (Dp44mT). This was investigated using intact red blood cells (RBCs), RBC lysates, purified oxyhemoglobin, and a mouse model. The chelation of cellular labile iron with the formation of a redox-active thiosemicarbazone-iron complex was found to be crucial for oxyhemoglobin oxidation. This observation was substantiated using a thiosemicarbazone that cannot ligate iron and also by using the chelator, desferrioxamine, that forms a redox-inactive iron complex. Of significance, cellular copper chelation was not important for metHb generation in contrast to its role in preventing tumor cell proliferation. Administration of Dp44mT to mice catalyzed metHb and cardiac metmyoglobin formation. However, ascorbic acid administered together with the drug in vivo significantly decreased metHb levels, providing a potential therapeutic intervention. Moreover, we demonstrated that the structure of the thiosemicarbazone is of importance in terms of metHb generation, because the DpT analog, di-2-pyridylketone-4-cyclohexyl-4-methyl-3-thiosemicarbazone (DpC), does not induce metHb generation in vivo. Hence, DpC represents a next-generation thiosemicarbazone that possesses markedly superior properties. This investigation is important for developing more effective thiosemicarbazone treatment regimens. PMID:22508546

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

    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.

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

    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

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

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

  5. Palladium(II) Complexes of NS Donor Ligands Derived from Steroidal Thiosemicarbazones as Antibacterial Agents

    Abdullah M. Asiri; Khan, Salman A

    2010-01-01

    We have investigated the antibacterial activity of some new steroidal thiosemicarbazones and their Pd(II) metal complexes were prepared by the reaction of the thiosemicarbazones with [Pd(DMSO)2Cl2]. The steroidal thiosemicarbazones were prepared by the reaction of thiosemicarbazides with a steroidal ketone. The structures of these compounds were elucidated by IR, 1H-NMR, 13C-NMR, FAB mass spectroscopic methods, elemental analyses and TGA analysis. The antibacterial activity of these compounds...

  6. Reactions with Visnaginone: Synthesis, Cyclisation and Microbial Evaluation of Some Visnaginone Thiosemicarbazone Derivatives

    Sadek Elsayed Abdou; Salah Mohamed El-Qusy; Sami Selim Ghabrial; Mahmoud Ibrahim Haggag

    2011-01-01

    Several new visnaginone ethers were prepared and their thiosemicarbazone derivatives  are  synthesized. The behavior of the thiosemicarbazones in methanolic sodium methoxide and hydrochloric acid is discussed. Structures were established on the bases of elemental and spectral data studies. Some of the thiosemicarbazones were tested for their antimicrobial activity. The structures of the synthesized derivatives (5a-g,6a-g) were confirmed by means of IR, 1H NMR, MS and elemental analyses. The s...

  7. The Effect of the Serum Amino Acid Levels Thiosemicarbazone Derivatives and its Metal Complexes on Rats

    Karatepe, Mustafa; Kaman, Dilara

    2013-01-01

    Advers biological activities of Thiosemicarbazone (TSC) and Schiff base (SB) derivatives have been widely studied in rats and in other animal species using different doses, times and routes of administration. To date, no attempt has been made to study alterations occurring in the amino acid profile in the effects of the thiosemicarbazone derivative and its metal complexes on the rats. At this study, the rats were injected subcutaneously with a new thiosemicarbazone and its LH-Zn and LH-Cu com...

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

    Marina Azevedo Souza; Susana Johann; Luciana Alves Rodrigues dos Santos Lima; Fernanda Fraga Campos; Isolda Castro Mendes; Heloisa Beraldo; Elaine Maria de Souza-Fagundes; Patricia Silva Cisalpino; Carlos Augusto Rosa; Tania Maria de Almeida Alves; Nivea Pereira de Sa; Carlos Leomar Zani

    2013-01-01

    Lapachol was chemically modified to obtain its thiosemicarbazone and semicarbazone derivatives. These compounds were tested for antimicrobial activity against several bacteria and fungi by the broth microdilution method. The thiosemicarbazone and semicarbazone derivatives of lapachol exhibited antimicrobial activity against the bacteria Enterococcus faecalis and Staphylococcus aureus with minimal inhibitory concentrations (MICs) of 0.05 and 0.10 µmol/mL, respectively. The thiosemicarbazone an...

  9. Antitrypanosomal Activity of Novel Benzaldehyde-Thiosemicarbazone Derivatives from Kaurenoic Acid †

    2011-01-01

    A series of new thiosemicarbazones derived from natural diterpene kaurenoic acid were synthesized and tested against the epimastigote forms of Trypanosoma cruzi to evaluate their antitrypanosomal potential. Seven of the synthesized thiosemicarbazones were more active than kaurenoic acid with IC50 values between 2-24.0 mM. The o-nitro-benzaldehyde-thiosemicarbazone derivative was the most active compound with IC50 of 2.0 mM. The results show that the structural modifications accomplished enhan...

  10. Synthesis, characterization and spectral studies of some lanthanide complexes with p-(methoxy or chloro) phenylglyoxal thiosemicarbazone

    The present work deals with the synthesis of trivalent Pr, Nd, Sm, Eu, Gd, Tb, Dy and Yb complexes of p-methoxyphenylglyoxal thiosemicarbazone (PMPGT) and p-chlorophenylglyoxal thiosemicarbazone (PCPGT). 15 refs., 2 tabs

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

    Present article is devoted to synthesis of complex compounds in the system [ReOG5]2--thiosemicarbazone acetone-Hg-acetone. The literature data on complex compounds of various metals with thiosemicarbazone was summarized. The synthesis of complex compounds in the system [ReOG5]2--thiosemicarbazone acetone-Hg-acetone was conducted. The complex compounds of rhenium with methyl ident thiosemicarbazone were synthesized.

  12. Improved cytotoxicity of pyridyl-substituted thiosemicarbazones against MCF-7 when used as metal ionophores.

    Akladios, Fady N; Andrew, Scott D; Parkinson, Christopher J

    2016-02-01

    Zinc is the second most abundant transition metal in the human body, between 3 and 10% of human genes encoding for zinc binding proteins. We have investigated the interplay of reactive oxygen species and zinc homeostasis on the cytotoxicity of the thiosemicarbazone chelators against the MCF-7 cell line. The cytotoxicity of thiosemicarbazone chelators against MCF-7 can be improved through supplementation of ionic zinc provided the zinc ion is at a level exceeding the thiosemicarbazone concentration. Elimination of the entire cell population can be accomplished with this regime, unlike the plateau of cytotoxicity observed on thiosemicarbazone monotherapy. The cytotoxic effects of copper complexes of the thiosemicarbazone are not enhanced by zinc supplementation, displacement of copper from the complex being disfavoured. Treatment of MCF-7 with uncomplexed thiosemicarbazone initiates post G1 blockade alongside the induction of apoptosis, cell death being abrogated through subsequent supplementation with zinc ion after drug removal. This would implicate a metal depletion mechanism in the cytotoxic effect of the un-coordinated thiosemicarbazone. The metal complexes of the species, however, fail to initiate similar G1 blockade and apparently exert their cytotoxic effect through generation of reactive oxygen species, suggesting that multiple mechanisms of cytotoxicity can be associated with the thiosemicarbazones dependant on the level of metal ion association. PMID:26683314

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

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

    2015-01-01

    selective in their inhibition of cathepsin L compared to cathepsin B. Thiosemicarbazone analogue 32 inhibited invasion through Matrigel of MDA-MB-231 breast cancer cells by 70% at 10μM. Thiosemicarbazone analogue 8 significantly inhibited the invasive potential of PC-3ML prostate cancer cells by 92% at 5μ...

  14. Vibrational spectra of palladium 5-nitrofuryl thiosemicarbazone complexes: Experimental and theoretical study

    Gambino, Dinorah; Otero, Lucía; Vieites, Marisol; Boiani, Mariana; González, Mercedes; Baran, Enrique J.; Cerecetto, Hugo

    2007-10-01

    The vibrational spectroscopic behavior of a series of 16 palladium(II) complexes with 8 bioactive nitrofuran containing thiosemicarbazones as ligands has been studied in the solid state. The IR and Raman spectra of these complexes and the free nitrofuran thiosemicarbazone ligands were recorded and analyzed. Experimental spectra were satisfactorily described by density functional theory (DFT) calculations. The combination of experimental and theoretical methods allowed us to perform the characterization of the main vibrations that show the mode of coordination of the thiosemicarbazone moiety to palladium even though these vibration bands are located in spectral regions showing a complicated pattern due to the presence of vibrations of the nitrofuran moiety and combination modes involving furan vibrations. A characteristic vibrational spectroscopic pattern has been defined for Pd(II) 5-nitrofuryl thiosemicarbazone complexes. This systematic knowledge may be useful for the analysis of the spectroscopic behavior of other coordination compounds holding the 5-nitrofuran thiosemicarbazone moiety.

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

    Georges C. Accrombessi

    2011-02-01

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

  16. Titanium zirconium and hafnium coordination compounds with vanillin thiosemicarbazone

    Coordination compounds of titanium zirconium and hafnium tetrachlorides with vanillin thiosemicarbazone of MCl4 x nLig composition, where n=1.5, 4 for titanium and 1, 2, 4 for zirconium and hafnium, are synthesized. Molar conductivity of ethanol solutions is measured; IR spectroscopic and thermochemical investigation are carried out. The supposition about ligand coordination via sulfur and azomethine nitrogen atoms is made. In all cases hafnium forms stable compounds than zirconium

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

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

  18. Some lanthanide complexes of semicarbazone and thiosemicarbazone derived from fluorenone

    A new series of lanthanide chloride complexes with the ligands fluorenone semicarbazone (FSC) and fluorenone thiosemicarbazone (FTSC) of composition [LnLCl2(H2O)2](Ln = La, Pr, Nd, Sm, Gd) were synthesised and characterized by microanalytical, spectral, magnetic and conductivity data. These ligands act as monovalent bidentate and bond through carbonyl oxygen/thiocarbonyl sulfur and the azomethine nitrogen atom. (author). 18 refs., 2 tabs

  19. Crystal structures of copper(II) complexes of 2-formylpyridine substituted thiosemicarbazones; the first example of a coordinated thiosemicarbazone with a thiol function

    West, D. X.; Swearingen, J. K.; Romack, T. J.; Billeh, I. S.; Jasinski, J. P.; Li, Y.; Staples, R. J.

    2001-08-01

    The crystal structures of two 5-coordinate copper(II) complexes containing neutral, tridentate 2-formylpyridine N(4)-substituted thiosemicarbazones have been determined. 2-Formylpyridine N(4)-cyclohexylthiosemicarbazone, HFo4CHex coordinates via the pyridine nitrogen, imine nitrogen and thione sulfur with two chloro ligands to produce [Cu(HFo4CHex)Cl 2]. Similarly, 2-formylpyridine 3-(4-methylpiperazine)thiosemicarbazone, HFoppz4M, produces [Cu(HFoppz4M)Cl 2] with one major difference; rather than the expected thione form of the thiosemicarbazone moiety, it coordinates as the thiol isomer. Both complexes are close to a square pyramid structure with axial and equatorial chloro ligands and the thiosemicarbazone moieties of both ligands nearly planar. Also included is the crystal structure of N-cyclohexylthiosemicarbazide, CHextsc.

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

    Marina Azevedo Souza

    2013-05-01

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

  1. Synthesis, characterization and biological evaluation of paeonol thiosemicarbazone analogues as mushroom tyrosinase inhibitors.

    Zhu, Tian-Hua; Cao, Shu-Wen; Yu, Yan-Ying

    2013-11-01

    A series of hydroxy- and methoxy-substituted paeonol thiosemicarbazone analogues were synthesized as potential tyrosinase inhibitors and their inhibitory effects on mushroom tyrosinase and inhibitory mechanism were evaluated. Paeonol thiosemicarbazone analogues have been found exhibiting more remarkable inhibition than their indexcompounds on mushroom tyrosinase. Among them, compound 2,4-dihydroxy acetophenone-4-phenyl-3-thiosemicarbazone (d1) had the most potent inhibition activity with the IC50 value of 0.006 ± 0.001 mM, displayed as a reversible competitive inhibitor. The inhibitory ability of o- or p-substituted acetophenone thiosemicarbazones was: di-substituted acetophenone thiosemicarbazones>mono-substituted acetophenone thiosemicarbazones>non-substituted acetophenone thiosemicarbazones. Copper ions chelation assay explained that compound d1 exhibited competitive inhibition by forming a chelate with the copper ions at the catalytic domain of tyrosinase as well as indicate a 1.5:1 binding ratio of compound d1 with copper ions. In the fluorescence spectrum study, compound d1 behaved stronger fluorescence quenching on tyrosinase towards d1-Cu(2+) complex, inhibiting tyrosinase mainly by means of chelating the two copper ions in the active site. The newly synthesized compounds may serve as structural templates for designing and developing novel tyrosinase inhibitors. PMID:24120880

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

    Souza, Marina Azevêdo; Johann, Susana; Lima, Luciana Alves Rodrigues dos Santos; Campos, Fernanda Fraga; Mendes, Isolda Castro; Beraldo, Heloisa; de Souza-Fagundes, Elaine Maria; Cisalpino, Patrícia Silva; Rosa, Carlos Augusto; Alves, Tânia Maria de Almeida; de Sá, Nívea Pereira; Zani, Carlos Leomar

    2013-01-01

    Lapachol was chemically modified to obtain its thiosemicarbazone and semicarbazone derivatives. These compounds were tested for antimicrobial activity against several bacteria and fungi by the broth microdilution method. The thiosemicarbazone and semicarbazone derivatives of lapachol exhibited antimicrobial activity against the bacteria Enterococcus faecalis and Staphylococcus aureus with minimal inhibitory concentrations (MICs) of 0.05 and 0.10 µmol/mL, respectively. The thiosemicarbazone and semicarbazone derivatives were also active against the pathogenic yeast Cryptococcus gattii (MICs of 0.10 and 0.20 µmol/mL, respectively). In addition, the lapachol thiosemicarbazone derivative was active against 11 clinical isolates of Paracoccidioides brasiliensis, with MICs ranging from 0.01-0.10 µmol/mL. The lapachol-derived thiosemicarbazone was not cytotoxic to normal cells at the concentrations that were active against fungi and bacteria. We synthesised, for the first time, thiosemicarbazone and semicarbazone derivatives of lapachol. The MICs for the lapachol-derived thiosemicarbazone against S. aureus, E. faecalis, C. gattii and several isolates of P. brasiliensis indicated that this compound has the potential to be developed into novel drugs to treat infections caused these microbes. PMID:23778660

  3. Aryl- and heteroaryl-thiosemicarbazone derivatives and their metal complexes: a pharmacological template.

    Moorthy, Narayana S H N; Cerqueira, Nuno M F S A; Ramos, Maria J; Fernandes, Pedro A

    2013-05-01

    In this review, we discuss the current patents concerning aryl/heteroaryl thiosemicarbazone derivatives as regards to their activities and properties, including coordination (chelation) properties. The mode of action of the aryl/heteroaryl thiosemicarbazone derivatives involves metal coordination with proteins or biological fluids that have metal ions in their structure. Additionally, these molecules can also form multiple hydrogen bonds through their (thio) amide and N3 nitrogen that ensure a strong interaction with the receptor. In some cases, strong π-π interactions can be observed too. Special attention is given to pyridyl, bis-pyridyl, benzoylpyridyl and isatin thiosemicarbazone derivatives that exhibit significant anticancer, antiviral and other activities in free and in metal complexed forms. This key biological role is often related with their capability to inhibit the enzyme ribonucleotide reductase, similar to what is observed with potent anticancer drugs such as Triapine and methisazone. Recent studies have revealed that thiosemicarbazone can also inhibit topoisomerase II α enzyme. Thiosemicarbazone derivatives form coordination complex with various metals such as Zn, Cu, Fe, Co, Ni, Pt, Pd, etc., and these complexes provide better activities than the free thiosemicarbazones. Recent patents show that the controlled or sustained release dosage form of the thiosemicarbazone derivatives along with ionizing radiations is used for the treatment of proliferative diseases (US20110152281, US20110245304, US20120172217). PMID:22963201

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

    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.

  5. SYNTHESIS AND BIOLOGICAL ACTIVITY OF BUTANONE THIOSEMICARBAZONE AND THEIR METALLIC COMPLEXES

    Sandeep Kumar; Nitin Kumar

    2013-01-01

    In present work, Ligand butanone thiosemicarbazone and their 11 complexes of the type ML2X2, ML2X’, where M = Cu(II), Cd(II), Co(II), Zn(II), Hg(II); L = butanone thiosemicarbazone; X = Cl, NO3 or CH3COO; X’ = SO4 have been synthesized and characterized with the help of infra-red and ultra-violet spectroscopy. The spectral data revealed that the thiosemicarbazone act as bidentate ligand, making use of thionic sulphur and the azomethine nitrogen atom for co-ordination to the central metal a...

  6. ESR, electrochemical and reactivity studies of antitrypanosomal palladium thiosemicarbazone complexes

    Otero, Lucía; Folch, Christian; Barriga, Germán; Rigol, Carolina; Opazo, Lucia; Vieites, Marisol; Gambino, Dinorah; Cerecetto, Hugo; Norambuena, Ester; Olea-Azar, Claudio

    2008-08-01

    Cyclic voltammetry (CV) and electron spin resonance (ESR) techniques were used in the investigation of novel palladium complexes with bioactive thiosemicarbazones derived from 5-nitrofurane or 5-nitrofurylacroleine. Sixteen palladium complexes grouped in two series of the formula [PdCl 2HL] or [PdL 2] were studied. ESR spectra of the free radicals obtained by electrolytic reduction were characterized and analyzed. The ESR spectra showed two different hyperfine patterns. The stoichiometry of the complexes does not seem to affect significantly the hyperfine constants however we observed great differences between 5-nitrofurane and 5-nitrofurylacroleine derivatives. The scavenger properties of this family of compounds were lower than Trolox.

  7. 4-(3-Fluorophenyl)-1-(propan-2-ylidene)thiosemicarbazone

    Barbara Miroslaw; Daniel Szulczyk; Anna E. Koziol; Marta Struga

    2011-01-01

    The title compound, C10H12FN3S, crystallizes in the same space group (P21/c) as two polymorphic forms of 4-phenyl-1-(propan-2-ylidene)thiosemicarbazone [Jian et al. (2005). Acta Cryst. E61, o653–o654; Venkatraman et al. (2005). Acta Cryst. E61, o3914–o3916]. The arrangement of molecules relative to the twofold screw axes is similar to that in the crystal structure of the lower density polymorph. In the solid state, the molecular conformation is stabilized by an intramolecu...

  8. Antimicrobial activity of some isatin-3--thiosemicarbazone complexes

    SANDRA S. KONSTANTINOVIC; Radovanovic, Blaga C.; Sovilj, Sofija P.; SVETLANA STANOJEVIC

    2008-01-01

    Isatin-3-thiosemicarbazone complexes with Co(II), Ni(II), Cu(II), Zn(II), Hg(II) and Pd(II) were synthesized and evaluated for their antimicrobial activity against 7 pathogenic bacteria and 4 fungi. The complexes have an enhanced activity compared to the ligand due to transition metal involved in coordination. The anti-amoebic activity in vitro was evaluated against the HM1:IMSS strain of Entamoeba histolytica and the results were compared with the standard drug, metronidazole. The preliminar...

  9. Reinvestigation of growth of urea thiosemicarbazone monohydrate crystal

    Srinivasan, Bikshandarkoil R.; Raghavaiah, Pallepogu; Nadkarni, V. S.

    2013-08-01

    The reaction of urea with thiosemicarbazide in 1:1 mole ratio in aqueous solution does not result in the formation of urea thiosemicarbazone monohydrate crystal, as reported by Hanumantharao, Kalainathan and Bhagavannarayana [Spectrochim. Acta A91 (2012) 345-351]. A reinvestigation of the reported reaction reveals that the crystal obtained is the starting material namely thiosemicarbazide, which has been unambiguously confirmed with the aid of infrared and 1H NMR spectra and single crystal X-ray structure determination. Analysis of 1H NMR spectrum reveals that thiosemicarbazide exhibits thione-thiol tautomerism in solution. In contrast, thiosemicarbazide exists as the thione tautomer in the solid state.

  10. ONE-POT SYNTHESIS OF FUNCTIONALIZED 2-THIAZOLIDIN-4-ONES FROM THIOSEMICARBAZONE DERIVATIVES AND ACETYLENIC ESTERS IN WATER Ein-Topf-Synthese funktionalisierter 2-THIAZOLIDIN-4-one FROM Thiosemicarbazone DERIVATE UND Acetylenische ESTERS IM WASSER.

    Sayed Ali Ahmadi*, Dadkhoda Ghazanfari

    2013-07-01

    Full Text Available Some derivatives of 2-thiazolidin-4-ones were synthesized from dialkyl acetylenedicarboxylates and thiosemicarbazone derivatives of chalchones in the presence of triphenylphosphine in water

  11. A spectral study of 2-formylimidazole 4N-substituted thiosemicarbazones and their copper(II) complexes

    West, Douglas X.; Lockwood, Mark A.; Albert, Julyan N.; Liberta, Anthony E.

    1993-11-01

    Copper(II) complexes of 2-formylimidazole 4N-methyl-, 4N-dimethyl- 4N-ethyl- and 3-hexa-methyleneiminylthiosemicarbazone, along with two nickel(II) complexes of the latter thiosemicarbazone, have been synthesized. Infrared, electronic, NMR and ESR spectra have been used to characterize the complexes and the uncomplexed thiosemicarbazones. None of the complexes or thiosemicarbazones possess growth inhibitory activity against Aspergillus niger and Paecilomyces variotii.

  12. Preparation and Biodistribution Studies of a Radiogallium-Acetylacetonate Bis (Thiosemicarbazone) Complex in Tumor-Bearing Rodents

    Jalilian, Amir Reza; Yousefnia, Hassan; SHAFAII, KAMALEDDIN; Novinrouz, Aytak; Rajamand, Amir Abbas

    2012-01-01

    Various radiometal complexes have been developed for tumor imaging, especially Ga-68 tracer. In the present study, the development of a radiogallium bis-thiosemicarbazone complex has been reported. [67Ga] acetylacetonate bis(thiosemicarbazone) complex ([67Ga] AATS) was prepared starting [67Ga]Gallium acetate and freshly prepared acetylacetonate bis (thiosemicarbazone) (AATS) in 30 min at 90°C. The partition co-efficient and the stability of the tracer were determined in final solution (25°C) ...

  13. Palladium(II Complexes of NS Donor Ligands Derived from Steroidal Thiosemicarbazones as Antibacterial Agents

    Abdullah M. Asiri

    2010-07-01

    Full Text Available We have investigated the antibacterial activity of some new steroidal thiosemicarbazones and their Pd(II metal complexes were prepared by the reaction of the thiosemicarbazones with [Pd(DMSO2Cl2]. The steroidal thiosemicarbazones were prepared by the reaction of thiosemicarbazides with a steroidal ketone. The structures of these compounds were elucidated by IR, 1H-NMR, 13C-NMR, FAB mass spectroscopic methods, elemental analyses and TGA analysis. The antibacterial activity of these compounds were tested in vitro by the disk diffusion assay against two Gram-positive and two Gram-negative bacteria. The results showed that steroidal complexes are better inhibitors of both types of the bacteria (Gram-positive and Gram-negative as compared to steroidal thiosemicarbazones. Compound Ia displays remarkable antibacterial activity as compared to amoxicillin.

  14. Synthesis of Novel Highly Functionalized 4-Thiazolidinone Derivatives from 4-Phenyl-3-thiosemicarbazones

    Abdelmadjid Benmohammed

    2014-03-01

    Full Text Available We present herein the synthesis in good yields of two series of highly functionalized thiazolidinone derivatives from the reactions of various 4-phenyl-3-thio-semicarbazones with ethyl 2-bromoacetate and diethyl acetylenedicarboxylate, respectively.

  15. Antitrypanosomal Activity of Novel Benzaldehyde-Thiosemicarbazone Derivatives from Kaurenoic Acid †

    Cecília M. A. de Oliveira

    2011-01-01

    Full Text Available A series of new thiosemicarbazones derived from natural diterpene kaurenoic acid were synthesized and tested against the epimastigote forms of Trypanosoma cruzi to evaluate their antitrypanosomal potential. Seven of the synthesized thiosemicarbazones were more active than kaurenoic acid with IC50 values between 2-24.0 mM. The o-nitro-benzaldehyde-thiosemicarbazone derivative was the most active compound with IC50 of 2.0 mM. The results show that the structural modifications accomplished enhanced the antitrypanosomal activity of these compounds. Besides, the thiocyanate, thiosemicarbazide and the p- methyl, p-methoxy, p-dimethylamine, m-nitro and o-chlorobenzaldehyde-thiosemicarbazone derivatives displayed lower toxicity for LLMCK2 cells than kaurenoic acid, exhibing an IC50 of 59.5 mM.

  16. Influence of anthraquinone scaffold on E/Z isomer distribution of two thiosemicarbazone derivatives. 2D NMR and DFT studies

    Marković, Violeta; Joksović, Milan D.; Marković, Svetlana; Jakovljević, Ivan

    2014-01-01

    A distribution of possible isomeric and tautomeric forms of two tautomerizable anthraquinone-thiosemicarbazones with pronounced cytotoxic potential was investigated using 2D NMR and DFT studies. Conformational analysis of the E and Z isomers of both thiosemicarbazones was performed to find out the most stable conformation for each molecule. It was found that superior stability of E-isomers results from ten-membered intramolecular hydrogen bond between thiosemicarbazone N2H and anthraquinone carbonyl group. This hydrogen bond is stronger than that between thiosemicarbazone N2H and ester oxygen, owing to the large partial negative charge on the anthraquinone oxygen.

  17. Microwave synthesis of mixed ligand diimine–thiosemicarbazone complexes of ruthenium(ii): biophysical reactivity and cytotoxicity†

    Beckford, Floyd A.; Shaloski, Michael; LeBlanc, Gabriel; Thessing, Jeffrey; Lewis-Alleyne, Lesley C.; Holder, Alvin A.; LI, LIYA; Seeram, Navindra P.

    2009-01-01

    A novel microwave-assisted synthetic method has been used to synthesise a series of mixed ligand ruthenium(ii) compounds containing diimine as well as bidentate thiosemicarbazone ligands. The compounds contain the diimine 1,10-phenanthroline (phen) or 2,2′-bipyridine (bpy) and the thiosemicarbazone is derived from 9-anthraldehyde. Based on elemental analyses and spectroscopic data, the compounds are best formulated as [(phen)2Ru(thiosemicarbazone)](PF6)2 and [(phen)2Ru(thiosemicarbazone)](PF6...

  18. Cyclopalladated organosilane-tethered thiosemicarbazones: novel strategies for improving antiplasmodial activity.

    Adams, Muneebah; Barnard, Linley; de Kock, Carmen; Smith, Peter J; Wiesner, Lubbe; Chibale, Kelly; Smith, Gregory S

    2016-04-01

    Two series of ferrocenyl- and aryl-derived cyclopalladated organosilane thiosemicarbazone complexes were synthesised via C-H bond activation. Selected compounds were evaluated for in vitro antiplasmodial activity against the chloroquine-sensitive (NF54) and chloroquine-resistant (Dd2) strains of the human malaria parasite Plasmodium falciparum. Cyclopalladation of the thiosemicarbazones resulted in antiplasmodial activities in the low micromolar range. PMID:26911403

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

    2013-01-01

    Lapachol was chemically modified to obtain its thiosemicarbazone and semicarbazone derivatives. These compounds were tested for antimicrobial activity against several bacteria and fungi by the broth microdilution method. The thiosemicarbazone and semicarbazone derivatives of lapachol exhibited antimicrobial activity against the bacteria Enterococcus faecalis and Staphylococcus aureus with minimal inhibitory concentrations (MICs) of 0.05 and 0.10 µmol/mL, respectively. The thiosemicarbazo...

  20. Transition metal quinone-thiosemicarbazone complexes 3: Spectroscopic characterizations of spin-mixed iron (III) of naphthoquinone-thiosemicarbazones

    Chikate, Rajeev C.; Padhye, Subhash B.

    2007-04-01

    An interesting series of iron (III) complexes with naphthoquinone-thiosemicarbazones are synthesized and physico-chemically characterized by elemental analysis, UV-vis, IR, EPR and magnetic susceptibility measurements. They possess a cationic octahedral [FeL 2] + species and a tetrahedral [FeCl 4] - anion and exhibit unusual spin-mixed states involving high-spin and low-spin ferric centers as revealed from magnetic behavior with significant amount of exchange interactions mediated by intermolecular associations. The magnetic susceptibility data is fitted with S=5/2 and S=1/2 Heisengberg's exchange coupled model; Hˆ=-2JSS and the magnetic exchange interactions are found to be of the order of -13.6 cm -1 indicating the moderate coupling between two paramagnetic centers present in different chemical and structural environment. The presence of spin-paired iron (III) cation having dxz2dxz2dxz1 ground state is revealed from the EPR spectra with three prominent peaks while the high-spin tetrahedral iron (III) anion exhibits characteristics g = 4 signal whose intensity increases with lowering the temperature suggesting its influence on the magnetic properties of the complex molecule. FTIR measurements indicate tridentate ONS donor systems involving quinone/hydroxyl oxygen, imine/hydrazinic nitrogen and thione/thiol sulfur atoms as binding sites for naphthoquinone-thiosemicarbazones.

  1. Antimicrobial activity of some isatin-3--thiosemicarbazone complexes

    SANDRA S. KONSTANTINOVIC

    2008-01-01

    Full Text Available Isatin-3-thiosemicarbazone complexes with Co(II, Ni(II, Cu(II, Zn(II, Hg(II and Pd(II were synthesized and evaluated for their antimicrobial activity against 7 pathogenic bacteria and 4 fungi. The complexes have an enhanced activity compared to the ligand due to transition metal involved in coordination. The anti-amoebic activity in vitro was evaluated against the HM1:IMSS strain of Entamoeba histolytica and the results were compared with the standard drug, metronidazole. The preliminary test results showed that the complexes had better anti-amoebic activity than their respective ligands. Moreover, the complexes showed better inhibition of the test organism.

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

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

    2008-11-01

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

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

    Two novel copper(II) complexes [Cu(HL)Cl]Cl.H2O (1) and [Cu(L)NO3]Ðœ‡H2O (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

  4. In vitro evaluation of the activity of thiosemicarbazone derivatives against mycotoxigenic fungi affecting cereals.

    Degola, Francesca; Morcia, Caterina; Bisceglie, Franco; Mussi, Francesca; Tumino, Giorgio; Ghizzoni, Roberta; Pelosi, Giorgio; Terzi, Valeria; Buschini, Annamaria; Restivo, Francesco Maria; Lodi, Tiziana

    2015-05-01

    With a steadily increasing world population, a more efficient system of food production is of paramount importance. One of the major causes of food spoilage is the presence of fungal pathogens and the production and accumulation of mycotoxins. In the present work we report a study on the activity of a series of functionalized thiosemicarbazones (namely cuminaldehyde, trans-cinnamaldehyde, quinoline-2-carboxyaldehyde, 5-fluoroisatin thiosemicarbazone and 5-fluoroisatin N(4)-methylthiosemicarbazone), as antifungal and anti-mycotoxin agents, against the two major genera of cereal mycotoxigenic fungi, i.e. Fusarium and Aspergillus. These thiosemicarbazones display different patterns of efficacy on fungal growth and on mycotoxin accumulation depending on the fungal species. Some of the molecules display a greater effect on mycotoxin synthesis than on fungal growth. PMID:25702884

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

    Mahjoub, Omima Abdalla; Farina, Yang

    2014-09-01

    Two novel copper(II) complexes [Cu(HL)Cl]Cl˙H2O (1) and [Cu(L)NO3]˙H2O (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.

  6. SYNTHESIS AND BIOLOGICAL ACTIVITY OF BUTANONE THIOSEMICARBAZONE AND THEIR METALLIC COMPLEXES

    Sandeep Kumar

    2013-01-01

    Full Text Available In present work, Ligand butanone thiosemicarbazone and their 11 complexes of the type ML2X2, ML2X’, where M = Cu(II, Cd(II, Co(II, Zn(II, Hg(II; L = butanone thiosemicarbazone; X = Cl, NO3 or CH3COO; X’ = SO4 have been synthesized and characterized with the help of infra-red and ultra-violet spectroscopy. The spectral data revealed that the thiosemicarbazone act as bidentate ligand, making use of thionic sulphur and the azomethine nitrogen atom for co-ordination to the central metal atom. All the compounds have been screened for their antibacterial activity against Gram positive bacteria Staphylococcus aureus, Staphylococcus epidermidis and Gram negative bacteria Escherichia coli and Pseudomonas aeruginosa. Some of complexes exhibited appreciable activity.

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

    Mahjoub, Omima Abdalla; Farina, Yang [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia)

    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.

  8. Spectroscopic evaluation of manganese(II) complexes derived from semicarbazones and thiosemicarbazones

    Chandra, Sulekh; Gupta, Lokesh Kumar

    2005-09-01

    Manganese(II) complexes having the general composition Mn(L) 2X 2 [where L = isopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC) and 4-aminoacetophenone thiosemicarbazone (LLD) and X = Cl -, 1/2SO 42-] have been synthesized. All the complexes were characterized by elemental analyses, molar conductance, magnetic moment susceptibility, EI-mass, 1H NMR, IR, EPR and electronic spectral studies. All the complexes show magnetic moments corresponding to five unpaired electrons. The possible geometries of the complexes were assigned on the basis of EPR, electronic and infrared spectral studies.

  9. Manganese(II) complexes of substituted di-2-pyridyl ketone thiosemicarbazones: Structural and spectral studies

    Philip, Varughese; Suni, V.; Kurup, Maliyeckal R. Prathapachandra; Nethaji, Munirathinam

    2006-05-01

    The reaction between manganese(II) acetate and two substituted thiosemicarbazones derived from di-2-pyridyl ketone (HL) in 1:2 molar ratio produces new complexes of general formula [MnL 2]. The thiosemicarbazone moiety in HL deprotonates and gets coordinated to Mn(II) through the azomethine nitrogen, one of the pyridyl nitrogens, and the thiolate sulfur in both the complexes. The crystal structure of [ MnL21] was established by single crystal X-ray diffraction and the compound crystallizes into a monoclinic lattice with P2 1/ c space group. Manganese(II) exists in a distorted octahedral geometry in the complexes.

  10. EPR, mass, IR, electronic, and magnetic studies on copper(II) complexes of semicarbazones and thiosemicarbazones

    Chandra, Sulekh; Gupta, Lokesh Kumar

    2005-01-01

    Copper(II) complexes having the general composition Cu(L) 2X 2 [where L = isopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC), and 4-aminoacetophenone thiosemicarbazone (LLD) and X = Cl -, 1/2SO 42-] have been synthesized. All the Cu(II) complexes reported here have been characterized by elemental analyses, molar conductance, magnetic moment susceptibility, EI mass, 1H NMR, IR, EPR, and electronic spectral studies. All the complexes were found to have magnetic moments corresponding to one unpaired electrons. The possible geometries of the complexes were assigned on the basis of EPR, electronic, and infrared spectral studies.

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

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

    2015-08-01

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

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

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

  13. 2-Hydroxy-4-n-butoxy-5-bromoacetophenone thiosemicarbazone as an extractive spectrophotometric reagent for nickel

    K N Patel; K. S. Parikh; Rashmin Manubhai Patel

    2011-01-01

    2-hydroxy-4-n-butoxy-5-bromoacetophenone thiosemicarbazone (HBBrAT) is spectrophotometric reagent for nickel (II) in chloroform. The metal ion reacts with 2-hydroxy-4-n-butoxy-5-bromoacetophenone thiosemicarbazone (HBBrAT) forming a dark brown coloured complex in the pH range 7.0-11.0. The complex shows maximum absorption at 440 nm. Beer’s law is obeyed in the range 2.74-6.86 µg/mL. The molar absorptivity and Sandell’s sensitivity are found to be 5229 Lmol-1cm-1 and 0.0105 &...

  14. Synthesis and thermal study of rhenium(V) coordination compounds with pyroracemic acid and phenylglyoxylic acid thiosemicarbazones

    One synthesized rhenium (V) coordination compounds with pyroracemic acid and phenylglyoxylic acid thiosemicarbazones at metal:ligand various ratios within 1-7 mole/l concentration hydrohalic acid media. On the basis of the package of the physical and chemical procedures one studied the synthesized composition and structure. By means of the thermogravimetry one studied the thermal stability of rhenium (V) coordination compounds with pyroracemic acid and phenylglyoxylic acid thiosemicarbazones, as well as that of rhenium (V) solvatocomplexes with pyroacemic acid thiosemicarbazone. One determined thermal decomposition mechanism of the coordination compounds: separation of the second sphere water, decarboxylizing and dehalogenation

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

    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.

  16. Synthesis, spectroscopic studies and crystal structure of ( E)-2-(2,4-dihydroxybenzylidene)thiosemicarbazone and ( E)-2-[(1 H-indol-3-yl)methylene]thiosemicarbazone

    Yıldız, Mustafa; Ünver, Hüseyin; Erdener, Diğdem; Kiraz, Aşkın; İskeleli, Nazan Ocak

    2009-02-01

    Thiosemicarbazone Schiff bases ( 1 and 2) derived from 2,4-dihydroxybenzaldehyde, indoline-3-carbaldehyde and thiosemicarbazone have been synthesized and their structures were elucidated by elemental analysis, FT-IR, 1H NMR, 13C NMR and UV-visible spectroscopic techniques. The structures of compounds 1 and 2 have also been examined cyrstallographically. The title compounds 1 and 2 crystallize in the monoclinic space group C2/ c and triclinic space group P1¯, with unit cell parameters: a = 21.421(1) and 7.233(1), b = 4.131(1) and 11.166(1), c = 24.942(2) and 13.648(1) Å, V = 1856.1(2) and 1019.5(1) Å 3, D x = 1.512 and 1.422 g cm -3 and Z = 8 and 4, respectively.

  17. Semicarbazonas e tiossemicarbazonas: o amplo perfil farmacológico e usos clínicos Semicarbazones and thiosemicarbazones: their wide pharmacological profile and clinical applications

    Heloisa Beraldo

    2004-01-01

    This article shows that thiosemicarbazones, semicarbazones and their metal complexes can exhibit target selectivity along with a wide pharmacological profile. Complexes of thiosemicarbazones with cytotoxic or antitumoral activity are presented, some of which show activity against cisplatinum-resistant cells. The inhibition mechanism of the enzyme ribonucleoside diphosphate reductase (RDR), involved in DNA syntheses, by alpha(N)-heterocyclic thiosemicarbazones is discussed. The encouraging res...

  18. Synthesis and Structure-Activity Correlation Studies of Metal Complexes of α-N-heterocyclic Carboxaldehyde Thiosemicarbazones in Shewanella oneidensis

    Quintell Tillison; Cedrick Whitaker; Ramaiyer Venkatraman; Wilson, Barbara A

    2005-01-01

    This investigation involved the synthesis of metal complexes to test the hypothesis that structural changes and metal coordination in pyridine thiosemicarbazones affect cell growth and cell proliferation in vitro. Thiosemicarbazones are well known to possess antitumor, antiviral, antibacterial, antimalarial, and other activities. Extensive research has been carried out on aliphatic, aromatic, heterocyclic and other types of thiosemicarbazones and their metal complexes. Due to the pronounced r...

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

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

    2006-01-01

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

  20. Insights into the binding of thiosemicarbazone derivatives with human serum albumin: spectroscopy and molecular modelling studies.

    Karthikeyan, Subramani; Bharanidharan, Ganesan; Kesherwani, Manish; Mani, Karthik Ananth; Srinivasan, Narasimhan; Velmurugan, Devadasan; Aruna, Prakasarao; Ganesan, Singaravelu

    2016-06-01

    4-[(1Z)-1-(2-carbamothioylhydrazinylidene)ethyl]phenyl acetate [Ace semi],4-[(1Z)-1-(2-carbamothioylhydrazinylidene)ethyl]phenyl propanoate [Pro semi] from the family of thiosemicarbazones derivative has been newly synthesized. It has good anticancer activity as well as antibacterial and it is also less toxic in nature, its binding characteristics are therefore of huge interest for understanding pharmacokinetic mechanism of the drug. The binding of thiosemicarbazone derivative to human serum albumin (HSA) has been investigated by studying its quenching mechanism, binding kinetics and the molecular distance (r) between donor (HSA) and acceptor (thiosemicarbazone derivative) was estimated according to Forster's theory of non-radiative energy transfer using fluorescence spectroscopy. The binding dynamics has been elaborated using synchronous fluorescence spectroscopy, and the feature of thiosemicarbazone derivative induced structural changes of HSA has been studied by circular dichorism, Fourier transform infrared spectroscopy. Molecular modelling simulations explore the hydrophobic interaction and hydrogen bonding which stabilizes the interaction. PMID:26368536

  1. Coordination compounds of succinate some 3d-metals with thiosemicarbazone furfurol

    In article the results of synthesis and investigations of the Ni (II), Co (II), Cu (II) and Zn succinates with thiosemicarbazone furfurol complexes were shown. The consistence, individuality, the pattern of coordination of apical ligand and the thermal behavior of obtained complexes were established. (author)

  2. The wide pharmacological versatility of semicarbazones, thiosemicarba-zones and their metal complexes.

    Beraldo, Heloisa; Gambino, Dinorah

    2004-01-01

    The more significant bioactivities of a variety of semicarbazones (anti-protozoa, anticonvulsant) and thiosemicarbazones (antibacterial, antifungal, antitumoral, antiviral) and their metal complexes are reviewed together with proposed mechanisms of action and structure-activity relationships. Clinical or potential pharmacological applications of these versatile compounds are discussed. PMID:14754441

  3. Coordination compounds of manganese(2) and cadmium(2) with α-ketoacid thiosemicarbazones

    Manganese (2) and cadmium (2) coordination compounds with gluoxalic, pyroacemic and benzoyl formic acid thiosemicarbazones are synthesized. ESR spectra of polycrystalline samples of manganese compounds and cadmium compounds activated with manganese at T=113 295 deg K allow to suppose that Mn2+ takes the position of Cd2+ ion which is in a weakly distorted octahedron crystal field

  4. Synthesis and Spectral Investigations of Some Platinum Metals Ions Coordination Compounds of 4[N-(Furan-2'-carboxalidene)Amino]Antipyrine Thiosemicarbazone and 4[N-(3',4',5'-Trimethoxybenzalidene)Amino]Antipyrine Thiosemicarbazone

    Ram K. Agarwal; PRASAD, Surendra

    2005-01-01

    The present work describes the synthesis and spectral properties of some platinum metals chlorides coordination compounds of 4[N-(-(furan-2'-carboxalidene)amino]antipyrine thiosemicarbazone (FFAAPTS) and 4[N-(3',4',5'-trimethoxybenzalidene)amino]antipyrine thiosemicarbazone (TMBAAPTS). All the compounds have the general composition MCl2(L) (M = Pd2+ or Pt2+ ; L = FFAAPTS or TMBAAPTS) or MCl3(L) (M = Ru3+ , Rh3+ or Ir3+ ; L = FFAAPTS or TMBAAPTS). All the complexes...

  5. Synthesis and structure-activity relationship study of a new series of antiparasitic aryloxyl thiosemicarbazones inhibiting Trypanosoma cruzi cruzain.

    Espíndola, José Wanderlan Pontes; Cardoso, Marcos Veríssimo de Oliveira; Filho, Gevanio Bezerra de Oliveira; Oliveira E Silva, Dayane Albuquerque; Moreira, Diogo Rodrigo Magalhaes; Bastos, Tanira Matutino; Simone, Carlos Alberto de; Soares, Milena Botelho Pereira; Villela, Filipe Silva; Ferreira, Rafaela Salgado; Castro, Maria Carolina Accioly Brelaz de; Pereira, Valéria Rego Alves; Murta, Silvane Maria Fonseca; Sales Junior, Policarpo Ademar; Romanha, Alvaro José; Leite, Ana Cristina Lima

    2015-08-28

    The discovery of new antiparasitic compounds against Trypanosoma cruzi, the etiological agent of Chagas disease, is necessary. Novel aryloxy/aryl thiosemicarbazone-based conformationally constrained analogs of thiosemicarbazones (1) and (2) were developed as potential inhibitors of the T. cruzi protease cruzain, using a rigidification strategy of the iminic bond of (1) and (2). A structure-activity relationship analysis was performed in substituents attached in both aryl and aryloxy rings. This study indicated that apolar substituents or halogen atom substitution at the aryl position improved cruzain inhibition and antiparasitic activity in comparison to unsubstituted thiosemicarbazone. Two of these compounds displayed potent inhibitory antiparasitic activity by inhibiting cruzain and consequently were able to reduce the parasite burden in infected cells and cause parasite cell death through necrosis. In conclusion, we demonstrated that conformational restriction is a valuable strategy in the development of antiparasitic thiosemicarbazones. PMID:26231082

  6. Synthesis and Crystal Structure of a Mn(Ⅱ) Complex with Thiosemicarbazone Derivative of Pyridine-3-carbaldehyde Showing Unusual Coordination Mode of Tridentate Thiosemicarbazone

    LI Ming-Xue; ZHOU Jing; WANG Jing-Ping; WANG Zi-Liang

    2006-01-01

    The title complex Mn(HL)4(NCS)2(CH3CH2OH)2 has been achieved via selfassembly by incorporating manganese(Ⅱ) into pyridine-3-carbaldehyde thiosemicarbazonate ligand,and characterized by elemental analysis and single-crystal X-ray diffraction study. The crystal crystallizes in triclinic, space group P1 with a = 8.896(2), b = 9.530(2), c = 14.520(4) (A), α =87.035(4), β= 88.112(4), γ= 69.434(4)°, V= 1150.9(5) (A)3, Z = 1, Mr = 984.17, Dc = 1.420 g/cm3,μ(MoKα) = 0.612 mm-1, F(000) = 511, the final R = 0.0574 and wR = 0.1547 for 2855 observed reflections with I > 2σ(I). The complex contains one six-coordinated manganese ion connected by two thiosemicarbazide ligands, in which the thiosemicarbazone ligand acts as a monodentate ligand and coordinates to the center metal atoms via the pyridyl nitrogen atoms, two ethanol molecules and two isothiocyanic anions to give rise to a mononuclear structure. The coordination of a potentially tridentate thiosemicarbazone in manganese(Ⅱ) complex without using its sulfur and imine nitrogen sites is unusual. Hydrogen bonds existing in the complex link the different components to stabilize the crystal structure.

  7. Ribonucleotide reductase inhibition by metal complexes of Triapine (3-aminopyridine-2-carboxaldehyde thiosemicarbazone): A combined experimental and theoretical study

    Popović-Bijelić, Ana; Kowol, Christian R.; Lind, Maria E S; Luo, Jinghui; Himo, Fahmi; Enyedy, Éva A.; Arion, Vladimir B.; Gräslund, Astrid

    2011-01-01

    Triapine (3-aminopyridine-2-carboxaldehyde thiosemicarbazone, 3-AP) is currently the most promising chemotherapeutic compound among the class of α-N-heterocyclic thiosemicarbazones. Here we report further insights into the mechanism(s) of anticancer drug activity and inhibition of mouse ribonucleotide reductase (RNR) by Triapine. In addition to the metal-free ligand, its iron(III), gallium(III), zinc(II) and copper (II) complexes were studied, aiming to correlate their cytotoxic activities wi...

  8. SPECTROSCOPIC AND BIOLOGICAL STUDIES OF SOME NEW COORDINATION COMPOUNDS OF TIN (II) AND (IV) WITH SEMICARBAZONES AND THIOSEMICARBAZONES.

    JITENDRA KUMAR RAWAT; HARI SHANKAR YADAV; A.K. VARSHNEY; Varshney, S.

    2012-01-01

    The present paper is a report on the synthesis of some new tin (II) and tin (IV) complexes by the reaction of stannous chloride and dimethyltin dichloride with semicarbazones and thiosemicarbazones using tetrahydrofuran(THF) as reaction medium. Semicarbazones and thiosemicarbazones used in these studies are synthesized by the condensation of 1-acetyl-2-naphthol, 2-acetyl-1-naphathol, 2-acetyl-5-methyl furan, 2-acetyl-4-methyl thiophene and 2-acetyl-naphthalene with ...

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

    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 ...

  10. Thiosemicarbazone complexes of the platinum metals. A story of variable coordination modes

    Indrani Pal; Falguni Basuli; Samaresh Bhattacharya

    2002-08-01

    Salicylaldehyde thiosemicarbazone (H2saltsc) reacts with [M(PPh3)3X2] (M = Ru, Os; X = Cl, Br) to afford complexes of type [M(PPh3)2(Hsaltsc)2], in which the salicylaldehyde thiosemicarbazone ligand is coordinated to the metal as a bidentate N,S-donor forming a four-membered chelate ring. Reaction of benzaldehyde thiosemicarbazones (Hbztsc-R) with [M(PPh3)3X2] also affords complexes of similar type, viz. [M(PPh3)2(bztsc-R)2], in which the benzaldehyde thiosemicarbazones have also been found to coordinate the metal as a bidentate N,S-donor forming a fourmembered chelate ring as before. Reaction of the Hbztsc-R ligands has also been carried out with [M(bpy)2X2] (M = Ru, Os; X = Cl, Br), which has afforded complexes of type [M(bpy)2(bztsc-R)]+, which have been isolated as perchlorate salts. Coordination mode of bztsc-R has been found to be the same as before. Structure of the Hbztsc-OMe ligand has been determined and some molecular modelling studies have been carried out determine the reason for the observed mode of coordination. Reaction of acetone thiosemicarbazone (Hactsc) has then been carried out with [M(bpy)2X2] to afford the [M(bpy)2(actsc)]ClO4 complexes, in which the actsc ligand coordinates the metal as a bidentate N,S-donor forming a five-membered chelate ring. Reaction of H2saltsc has been carried out with [Ru(bpy)2Cl2] to prepare the [Ru(bpy)2(Hsaltsc)]ClO4 complex, which has then been reacted with one equivalent of nickel perchlorate to afford an octanuclear complex of type [{Ru(bpy)2(saltsc-H)}4Ni4](ClO4)4.

  11. [Differentiation activity of pyridoxal thiosemicarbazone and its copper and cobalt complexes on Friend erythroleukemia cells].

    Albertini, R; Gasparri Fava, G; Pinelli, S; Tarasconi, P; Starcich, B

    1991-07-01

    Thiosemicarbazones are a wide group of organic derivatives whose biological activities are a function of the parent aldehyde or ketone and of the coordination metal type. Some thiosemicarbazones possess a broad spectrum of potentially useful chemotherapeutic properties (antitumor, antibacterial, antiviral, antimalarial). The present study reports the biological effects of pyridoxal thiosemicarbazone, H2L, and relative complexes with copper, [(Cu(HL)(OH2))2]++ and with cobalt, [Co(III)(L)(HL)] on the differentiation of Friend erythroleukemia cells (FLC). They are murine proerythroblasts chronically infected by a producing Friend leukemia virus complex; their exposure to dimethylsulfoxide (Me2SO) or other chemical agents induces these cells to terminal erythroid differentiation, therefore these cells represent a good model of differentiation in vitro. Here we describe induction differentiation experiment of pyridoxal thiosemicarbazone and relative complexes of copper and cobalt on FLC performed with concentrations of 50 ug/ml (ligand), 2 ug/ml (complexes). These have little effects on cell proliferation at doses used in these experiments. Higher doses have evident cytotoxic effects. The treatment with the copper complex induces a moderate differentiation of FLC and enhances effects on erythroid differentiation of Me2SO-induced FLC. On the contrary H2L and [Co(III)(L)(HL)] haven't inducing effects or enhancing effects on Me2SO-induced FLC hemopoietic differentiation. In conclusion, the present study shows that copper complexes of pyridoxal thiosemicarbazone exert action of inducing agent and are able to enhance Me2SO-induced FLC hemopoietic differentiation. PMID:1818592

  12. Synthesis and structure-activity correlation studies of metal complexes of alpha-N-heterocyclic carboxaldehyde thiosemicarbazones in Shewanella oneidensis.

    Wilson, Barbara A; Venkatraman, Ramaiyer; Whitaker, Cedrick; Tillison, Quintell

    2005-04-01

    This investigation involved the synthesis of metal complexes to test the hypothesis that structural changesand metal coordination in pyridine thiosemicarbazones affect cell growth and cell proliferation in vitro. Thiosemicarbazones are well known to possess antitumor, antiviral, antibacterial, antimalarial, and other activities. Extensive research has been carried out on aliphatic, aromatic, heterocyclic and other types of thiosemicarbazones and their metal complexes. Due to the pronounced reactivity exhibited by metal complexes of heterocyclic thiosemicarbazones, synthesis and structural characterization of di-2-pyridylketone 4N-phenyl thiosemicarbazone and diphenyl tin (Sn) and platinum (Pt) complexes were undertaken. Shewanella oneidensis MR-1, a metal ion-reducing bacterium, was used as a model organism to explore the biological activity under aerobic conditions. A comparision of the cytotoxic potential of selected ligand and metal-complex thiosemicarbazones on cell growth in wild type MR-1 and mutant DSP-010 Shewanella oneidensis strains at various concentrations (0, 5, 10, 15, 20 or 25 ppm) was performed. The wild type (MR-1) grown in the presence of increasing concentrations of Sn- thiosemicarbazone complexes was comparatively more sensitive (mean cell number = 4.8 X 10(8) +/- 4.3 X 10(7) SD) than the DSP-010, a spontaneous rifampicillin derivative of the parent strain (mean cell number = 5.6 x 10(8) +/- 6.4 X 10(7) SD) under comparable aerobic conditions (p = 0.0004). No differences were observed in the sensitivity of the wild and mutant types when exposed to various concentrations of diphenyl Pt- thiosemicarbazone complex (p = 0.425) or the thiosemicarbazone ligand (p = 0.313). Growth of MR-1 in the presence of diphenyl Sn-thiosemicarbazone was significantly different among treatment groups (p = 0.012). MR-1 cell numbers were significantly higher at 5ppm than at 10 to 20ppm (p = 0.05). The mean number of DSP-010 variant strain cells also differed among

  13. Synthesis and Structure-Activity Correlation Studies of Metal Complexes of α-N-heterocyclic Carboxaldehyde Thiosemicarbazones in Shewanella oneidensis

    Wilson, Barbara A.; Venkatraman, Ramaiyer; Whitaker, Cedrick; Tillison, Quintell

    2005-01-01

    This investigation involved the synthesis of metal complexes to test the hypothesis that structural changes and metal coordination in pyridine thiosemicarbazones affect cell growth and cell proliferation in vitro. Thiosemicarbazones are well known to possess antitumor, antiviral, antibacterial, antimalarial, and other activities. Extensive research has been carried out on aliphatic, aromatic, heterocyclic and other types of thiosemicarbazones and their metal complexes. Due to the pronounced reactivity exhibited by metal complexes of heterocyclic thiosemicarbazones, synthesis and structural characterization of di-2-pyridylketone 4N-phenyl thiosemicarbazone and diphenyl tin (Sn) and platinum (Pt) complexes were undertaken. Shewanella oneidensis MR-1, a metal ion-reducing bacterium, was used as a model organism to explore the biological activity under aerobic conditions. A comparision of the cytotoxic potential of selected ligand and metal-complex thiosemicarbazones on cell growth in wild type MR-1 and mutant DSP-010 Shewanella oneidensis strains at various concentrations (0, 5, 10, 15, 20 or 25 ppm) was performed. The wild type (MR-1) grown in the presence of increasing concentrations of Sn- thiosemicarbazone complexes was comparatively more sensitive (mean cell number = 4.8 × 108 ± 4.3 × 107 SD) than the DSP-010, a spontaneous rifampicillin derivative of the parent strain (mean cell number = 5.6 × 108 ± 6.4 × 107 SD) under comparable aerobic conditions (p=0.0004). No differences were observed in the sensitivity of the wild and mutant types when exposed to various concentrations of diphenyl Pt- thiosemicarbazone complex (p= 0.425) or the thiosemicarbazone ligand (p=0.313). Growth of MR-1 in the presence of diphenyl Sn- thiosemicarbazone was significantly different among treatment groups (p=0.012). MR-1 cell numbers were significantly higher at 5ppm than at 10 to 20ppm (p = 0.05). The mean number of DSP-010 variant strain cells also differed among diphenyl Sn

  14. Antibacterial Evaluation of Some Schiff Bases Derived from 2-Acetylpyridine and Their Metal Complexes

    Thong Kwai Lin

    2012-05-01

    Full Text Available A series of Schiff bases derived from 2-acetylpyridne and their metal complexes were characterized by elemental analysis, NMR, FT-IR and UV-Vis spectral studies. The complexes were screened for anti-bacterial activity against Methicillin-resistant Staphylococcus aureus (MRSA, Acinetobacter baumanni (AC, Klebsiella pneumonie (KB and Pseudomonas aeruginosa (PA using the disc diffusion and micro broth dilution assays. Based on the overall results, the complexes showed the highest activities against MRSA while a weak antibacterial activity was observed against A. baumanii and P. aeruginosa.

  15. Antibacterial Evaluation of Some Schiff Bases Derived from 2-Acetylpyridine and Their Metal Complexes

    Thong Kwai Lin; Chai Lay Ching; Cher Lin Ooi; Hadi, A. Hamid A.; Mahmood Ameen Abdulla; Nura Suleiman Gwaram; Hapipah Mohd Ali; Hamid Khaledi

    2012-01-01

    A series of Schiff bases derived from 2-acetylpyridne and their metal complexes were characterized by elemental analysis, NMR, FT-IR and UV-Vis spectral studies. The complexes were screened for anti-bacterial activity against Methicillin-resistant Staphylococcus aureus (MRSA), Acinetobacter baumanni (AC), Klebsiella pneumonie (KB) and Pseudomonas aeruginosa (PA) using the disc diffusion and micro broth dilutio...

  16. Antibacterial evaluation of some Schiff bases derived from 2-acetylpyridine and their metal complexes.

    Gwaram, Nura Suleiman; Ali, Hapipah Mohd; Khaledi, Hamid; Abdulla, Mahmood Ameen; Hadi, A Hamid A; Lin, Thong Kwai; Ching, Chai Lay; Ooi, Cher Lin

    2012-01-01

    A series of Schiff bases derived from 2-acetylpyridne and their metal complexes were characterized by elemental analysis, NMR, FT-IR and UV-Vis spectral studies. The complexes were screened for anti-bacterial activity against Methicillin-resistant Staphylococcus aureus (MRSA), Acinetobacter baumanni (AC), Klebsiella pneumonie (KB) and Pseudomonas aeruginosa (PA) using the disc diffusion and micro broth dilution assays. Based on the overall results, the complexes showed the highest activities against MRSA while a weak antibacterial activity was observed against A. baumanii and P. aeruginosa. PMID:22609786

  17. Synthesis, Crystal Structural Investigations, and DFT Calculations of Novel Thiosemicarbazones

    Brian J. Anderson

    2016-02-01

    Full Text Available The crystal and molecular structures of three new thiosemicarbazones, 2-[1-(2-hydroxy-5-methoxyphenylethylidene]-N-methyl-hydrazinecarbothioamide monohydrate (1, 2-[1-(2-hydroxy-5-methoxyphenylethylidene]-N-ethyl-hydrazinecarbothioamide (2 and 2-[1-(2-hydroxy-4-methoxyphenylethylidene]-N-ethyl-hydrazinecarbothioamide acetonitrile solvate (3, are reported and confirmed by single crystal X-ray diffraction, NMR and UV-vis spectroscopic data. Compound (1, C11H15N3O2S·H2O, crystallizes in the monoclinic with space group P21/c, with cell parameters a = 8.2304(3 Å, b = 16.2787(6 Å, c = 9.9708(4 Å, and β = 103.355(4°. Compound (2, C12H17N3O2S, crystallizes in the C2/c space group with cell parameters a = 23.3083(6 Å, b = 8.2956(2 Å, c = 13.5312(3 Å, β = 91.077(2°. Compound (3, C11H15N3O2S·C2H3N, crystallizes in the triclinic P-1 space group with cell constants a = 8.9384(7 Å, b = 9.5167(8 Å, c = 10.0574(8 Å, α = 110.773(7°, β = 92.413(6°, and γ = 90.654(7°. DFT B3LYP/6-31(G geometry optimized molecular orbital calculations were also performed and frontier molecular orbitals of each compound are displayed. The correlations between the calculated molecular orbital energies (eV for the surfaces of the frontier molecular orbitals to the electronic excitation transitions from the absorption spectra of each compound have been proposed. Additionally, similar correlations observed among three closely related compounds, (4, 2-[1-(2-hydroxy-4-methoxyphenylethylidene]-N-methyl-hydrazinecarbothioamide, (5, 2-[1-(2-hydroxy-6-methoxyphenylethylidene]-N-methyl-hydrazinecarbothioamide acetonitrile monosolvate and (6, 2-[1-(2-hydroxy-6-methoxyphenylethylidene]-N-ethyl-hydrazinecarbothioamide, examining structural differences from the substitution of the methoxy group from the phenyl ring (4, 5, or 6 position and the substitution of the terminal amine (methyl or ethyl to their frontier molecular orbital surfaces and from their Density Functional

  18. Complexes of 3dn Metal Ions with Thiosemicarbazones: Synthesis and Antimicrobial Activity

    Tudor Rosu

    2007-04-01

    Full Text Available The chelating behavior of the thiosemicarbazone derivatives of 2-hydroxy-8-R-tricyclo[7.3.1.0.2,7]tridecane-13-one (where R = H, CH3, C6H5 towards Co(II, Ni(II and Cu(II has been investigated by elemental analysis, molar conductivity measurements, UV-VIS, IR, ESR spectroscopy and thermal studies. It was deduced from the experiments performed that the ligands coordinate to metal ions in different ways – neutral bidentate or mononegative bidentate – depending on the nature of R. Also, if metal acetates are used instead of metal chlorides, the ligands coordinate in a mononegative bidentate fashion, regardless of the nature of R or the thiosemicarbazone type ligand. The antimicrobial activity of the ligands and of the complexes towards samples of Acinetobacter boumanii, Klebsiella pneumoniae, Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa was determined.

  19. Spectroscopic and biological studies on newly synthesized nickel(II) complexes of semicarbazones and thiosemicarbazones

    Chandra, Sulekh; Gupta, Lokesh Kumar

    2005-12-01

    Nickel(II) complexes, having the general composition Ni(L) 2X 2, have been synthesized [where L: isopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC) and 4-aminoacetophenone thiosemicarbazone (LLD) and X = Cl -, 1/2SO 42-]. All the Ni(II) complexes reported here have been characterized by elemental analyses, magnetic moments, IR, electronic and mass spectral studies. All the complexes were found to have magnetic moments corresponding to two unpaired electrons. The possible geometries of the complexes were assigned on the basis of electronic and infrared spectral studies. Newly synthesized ligand and its nickel(II) complexes have been screened against different bacterial and fungal growth.

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

    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

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

    Yanmin Huang

    2015-01-01

    Full Text Available 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.

  2. Structural studies on acetophenone- and benzophenone-derived thiosemicarbazones and their zinc(II) complexes

    Ferraz, Karina S. O.; Silva, Nayane F.; Da Silva, Jeferson G.; Speziali, Nivaldo L.; Mendes, Isolda C.; Beraldo, Heloisa

    2012-01-01

    In the present work N(3)- meta-chlorophenyl-(HAc3 mCl, 1) and N(3)- meta-fluorphenyl-(HAc3 mF, 2) acetophenone thiosemicarbazone, and N(3)- meta-chlorophenyl-(HBz3 mCl, 3) and N(3)- meta-fluorphenyl-(HBz3 mF, 4) benzophenone thiosemicarbazone were obtained, as well as their zinc(II) complexes [Zn(Ac3 mCl) 2] ( 5), [Zn(Ac3 mF) 2] ( 6), [Zn(Bz3 mCl) 2] ( 7) and [Zn(Bz3 mF) 2] ( 8). Upon re-crystallization in DMSO:acetone conversion of 8 into [Zn(Bz3 mF) 2]·(DMSO) ( 8a) occurred. The crystal structures of 2, 5 and 8a were determined.

  3. Synergistic extraction of uranium(VI) by 2-hydroxy-1-naphthaldehyde thiosemicarbazone and several neutral donors

    The extraction behaviour of U (VI) from an aqueous nitric acid medium employing a 2-hydroxy-1-naphthaldehyde thiosemicarbazone in ethyl acetate has been studied in presence of different neutral donors like trioctyl phosphine oxide (TOPO), dimethyl sulphoxide (DMSO) and trioctyl amine (TOA). The extraction constant (log kex) for the binary organic phases UO2.A.X (where A = ligand, X = NO3-1) was found to be 1.976 which is by far the largest value amongst known values for the thiosemicarbazone. The overall equilibrium constant (log K) for the ternary complexes UO2A(NO3).TOPO, UO2A(NO3).TOA and UO2A(NO3).DMSO were estimated to be 6.06, 6.77 and 4.95, respectively. The effect of different diluents on the extraction behaviour has also been studied. (orig.)

  4. Deposition of rod-shaped antimony sulfide thin films from single-source antimony thiosemicarbazone precursors

    Biswal, Jasmine B.; Sawant, Narayan V. [Department of Chemistry, University of Mumbai, Vidyanagari, Santacruz (East), Mumbai - 400 098 (India); Garje, Shivram S., E-mail: ssgarje@chem.mu.ac.i [Department of Chemistry, University of Mumbai, Vidyanagari, Santacruz (East), Mumbai - 400 098 (India)

    2010-04-02

    Antimony sulfide thin films were deposited on glass substrates by aerosol assisted chemical vapour deposition technique using single source precursors, namely, antimony(III) thiosemicarbazones, SbCl{sub 3}(L) (L = thiosemicarbazones of thiophene-2-carboxaldehyde (1) and cinnamaldehyde (2)). The deposited films were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis and UV-visible spectroscopy in order to identify their phases, morphologies, compositions and optical properties respectively. These characterizations revealed that the films were comprised of rod-shaped particles of orthorhombic stibnite (Sb{sub 2}S{sub 3}) with a Sb:S stoichiometry of {approx} 1:1.3. The calculated optical band gap from UV-vis absorption spectrum is found to be 3.48 eV.

  5. Design, synthesis and biological evaluation of new aryl thiosemicarbazone as antichagasic candidates.

    Blau, Lorena; Menegon, Renato Farina; Trossini, Gustavo H G; Molino, João Vitor Dutra; Vital, Drielli Gomes; Cicarelli, Regina Maria Barretto; Passerini, Gabriela Duó; Bosquesi, Priscila Longhin; Chin, Chung Man

    2013-09-01

    The present work reports on the synthesis, biological assaying and docking studies of a series of 12 aryl thiosemicarbazones, which were planned to act over two main enzymes, cruzain and trypanothione reductase. These enzymes are used as targets of trypanocidal activity in Chagas disease control with a minimal mutagenic profile. Three p-nitroaromatic thiosemicarbazones showed high activity against Trypanosoma cruzi in in vitro assays (IC50 < 57 μM), and no mutagenic profile was observed in micronucleous tests. Although the in vitro inhibition test showed that 10-μM doses of eight compounds inhibited cruzain activity, no correlation was found between cruzain inhibition and trypanocidal activity. PMID:23851115

  6. Synthesis, molecular modeling, and biological evaluation of novel chiral thiosemicarbazone derivatives as potent anticancer agents.

    Taşdemir, Demet; Karaküçük-İyidoğan, Ayşegül; Ulaşli, Mustafa; Taşkin-Tok, Tuğba; Oruç-Emre, Emİne Elçİn; Bayram, Hasan

    2015-02-01

    A series of new chiral thiosemicarbazones derived from homochiral amines in both enantiomeric forms were synthesized and evaluated for their in vitro antiproliferative activity against A549 (human alveolar adenocarcinoma), MCF-7 (human breast adenocarcinoma), HeLa (human cervical adenocarcinoma), and HGC-27 (human stomach carcinoma) cell lines. Some of compounds showed inhibitory activities on the growth of cancer cell lines. Especially, compound exhibited the most potent activity (IC50 4.6 μM) against HGC-27 as compared with the reference compound, sindaxel (IC50 10.3 μM), and could be used as a lead compound to search new chiral thiosemicarbazone derivatives as antiproliferative agents. PMID:25399965

  7. Monitoring cellular uptake and cytotoxicity of copper(II) complex using a fluorescent anthracene thiosemicarbazone ligand.

    Kate, Anup N; Kumbhar, Anupa A; Khan, Ayesha A; Joshi, Pranaya V; Puranik, Vedavati G

    2014-01-15

    The thiosemicarbazone derivative of anthracene (ATSC, anthracene thiosemicarbazone 1) and its copper(II) complex (CuATSC, 2) were synthesized and characterized by spectroscopic, electrochemical, and crystallographic techniques. Interaction of 1 and 2 with calf thymus (CT) DNA was explored using absorption and emission spectral methods, and viscosity measurements reveal a partial-intercalation binding mode. Their protein binding ability was monitored by the quenching of tryptophan emission using bovine serum albumin (BSA) as a model protein. Furthermore, their cellular uptake, in vitro cytotoxicity testing on the HeLa cell line, and flow cytometric analysis were carried out to ascertain the mode of cell death. Cell cycle analysis indicated that 1 and 2 cause cell cycle arrest in sub-G1 phase. PMID:24328322

  8. Spectroscopic, thermal and electrochemical studies on some nickel(II) thiosemicarbazone complexes

    El-Shazly, R. M.; Al-Hazmi, G. A. A.; Ghazy, S. E.; El-Shahawi, M. S.; El-Asmy, A. A.

    2005-01-01

    Several complexes of thiosemicarbazone derivatives with Ni(II) have been prepared. Structural investigation of the ligands and their complexes has been made based on elemental analysis, magnetic moment, spectral (UV-Vis, i.r., 1H NMR, ms), and thermal studies. The i.r. spectra suggest the bidentate mononegative and tridentate (neutral, mono-, and binegative) behavior of the ligands. Different stereochemistries were suggested for the isolated complexes. The thermogravimetry (TG) and derivative thermogravimetry (DTG) have been used to study the thermal decomposition and kinetic parameters of some ligands and complexes using the Coats-Redfern and Horowitz-Metzger equations. The redox properties and stability of the complexes toward oxidation waves explored by cyclic voltammetry are related to the electron withdrawing or releasing ability of the substituent of thiosemicarbazone moiety. The samples displayed Ni II/Ni I couples irreversible waves associated with Ni III/Ni II process.

  9. Synergistic extraction of uranium(VI) by 2-hydroxy-1-naphthaldehyde thiosemicarbazone and several neutral donors

    Banerjee, S.; Bhar, M.; Basu, S. [Dept. of Chemistry, The Univ. of Burdwan, Golapbag, Burdwan (India)

    2003-07-01

    The extraction behaviour of U (VI) from an aqueous nitric acid medium employing a 2-hydroxy-1-naphthaldehyde thiosemicarbazone in ethyl acetate has been studied in presence of different neutral donors like trioctyl phosphine oxide (TOPO), dimethyl sulphoxide (DMSO) and trioctyl amine (TOA). The extraction constant (log k{sub ex}) for the binary organic phases UO{sub 2}.A.X (where A = ligand, X = NO{sub 3}{sup -1}) was found to be 1.976 which is by far the largest value amongst known values for the thiosemicarbazone. The overall equilibrium constant (log K) for the ternary complexes UO{sub 2}A(NO{sub 3}).TOPO, UO{sub 2}A(NO{sub 3}).TOA and UO{sub 2}A(NO{sub 3}).DMSO were estimated to be 6.06, 6.77 and 4.95, respectively. The effect of different diluents on the extraction behaviour has also been studied. (orig.)

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

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

    2015-08-01

    Urease is an important enzyme which breaks urea into ammonia and carbon dioxide during metabolic processes. However, an elevated activity of urease causes various complications of clinical importance. The inhibition of urease activity with small molecules as inhibitors is an effective strategy for therapeutic intervention. Herein, we have synthesized a series of 19 benzofurane linked N-phenyl semithiocarbazones (3a-3s). All the compounds were screened for enzyme inhibitor activity against Jack bean urease. The synthesized N-phenyl thiosemicarbazones had varying activity levels with IC50 values between 0.077 ± 0.001 and 24.04 ± 0.14 μM compared to standard inhibitor, thiourea (IC50 = 21 ± 0.11 μM). The activities of these compounds may be due to their close resemblance of thiourea. A docking study with Jack bean urease (PDB ID: 4H9M) revealed possible binding modes of N-phenyl thiosemicarbazones. PMID:26119990

  11. Microwave-Assisted Synthesis of New N1,N4-Substituted Thiosemicarbazones

    Aurea Echevarria

    2011-12-01

    Full Text Available We present an efficient procedure for the synthesis of thirty-six N1,N4-substituted thiosemicarbazones, including twenty-five ones that are reported for the first time, using a microwave-assisted methodology for the reaction of thiosemicarbazide intermediates with aldehydes in the presence of glacial acetic acid in ethanol and under solvent free conditions. Overall reaction times (20–40 min when ethanol as solvent, and 3 min under solvent free conditions were much shorter than with the traditional procedure (480 min; satisfactory yields and high-purity compounds were obtained. The thiosemicarbazide intermediates were obtained from alkyl or aryl isothiocyanates and hydrazine hydrate or phenyl hydrazine by stirring at room temperature for 60 min or by microwave irradiation for 30 min, with lower yields for the latter. The preliminary in vitro antifungal activity of thiosemicarbazones was evaluated against Aspergillus parasiticus and Candida albicans.

  12. Avaliação do potencial anticorrosivo de tiossemicarbazonas solubilizadas em microemulsão Evaluation of anticorrosive effectiveness of thiosemicarbazones solubilized in a microemulsion system

    Elaine Cristina M. de Moura

    2013-01-01

    Full Text Available In this paper, thiosemicarbazones 4-N-cinnamoyl-thiosemicarbazone (CTSC, 4-N-(2'-methoxycinnamoyl-thiosemicarbazone (MCTSC, and 4-N-(4'-hydroxy-3'-methoxybenzoyl- thiosemicarbazone (HMBTSC were solubilized in an oil-in-water (O/W microemulsion system (ME_OCS, forming systems CTSC_ME_OCS, MCTSC_ME_OCS and HMBTSC_ME_OCS. The effectiveness of these systems in the process of inhibiting AISI 1020 carbon steel corrosion was evaluated in a saline solution (NaCl 0.5%, using a galvanostatic method. The tested thiosemicarbazones showed higher inhibitory effects (85.7% for CTSC_ME_OCS, 84.0% for MCTSC_ME_OCS, and 83.3% for HMBTSC_ME_OCS. The surfactant OCS (dissolved in H2O and the ME_OCS system showed lower efficacies, with 71.0% for OCS and 74.0% for ME_OCS system.

  13. Spectroscopic, Thermal and Biological Studies on Some Trivalent Ruthenium and Rhodium NS Chelating Thiosemicarbazone Complexes

    Vinod K Sharma; Shipra Srivastava; Ankita Srivastava

    2007-01-01

    The synthetic, spectroscopic, and biological studies of sixteen ring-substituted 4-phenylthiosemicarbazones and 4-nitrophenyl-thiosemicarbazones of anisaldehyde, 4-chlorobenzaldehyde, 4-fluorobenzaldehyde, and vanillin with ruthenium(III) and rhodium(III) chlorides are reported here. Their structures were determined on the basis of the elemental analyses, spectroscopic data (IR, electronic, 1H and 13C NMR) along with magnetic susceptibility measurements, molar conductivity and thermogravimetr...

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

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

    2004-01-01

    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 snai...

  15. The Hypolipidemic Activity of Heterocyclic Thiosemicarbazones, Thioureas and Their Metal Complexes in Sprague Dawley Male Rats

    Hall, Iris H.; Chen, S. Y.; Barnes, Betsy Jo; West, Douglas X.

    1999-01-01

    Heterocyclic thiosemicarbazones, thioureas and their copper, nickel, and cobalt complexes were shown to be potent hypolipidemic agents in male Sprague Dawley rats at 8 mg/kg/day, orally. These agents lowered the activity of rat hepatic rate limiting enzymes for the synthesis of cholesterol and triglycerides. The effects of these agnets on cytoplasmic ATP-dependent citrate lyase, acetyl CoA synthetase and HMG-CoA reductase activities were reduced by a magnitude to explain the reduction of seru...

  16. Dioxouranium (VI) complexes of N4- substituted aryl thiosemicarbazones derived from 2,6- diacetylpyridine

    Some seven-coordinated dioxouranium(VI) complexes of 4N-aryl substituted thiosemicarbazones derived from 2,6-diacetylpyridine were prepared in non-aqueous solvent. All the complexes were characterised by infrared, electronic and 1H NMR spectra. In all the cases the ligands behave as di basic quinquedentate (N3S2) ligands. The complexes may have distorted pentagonal bipyramidal geometry. (author)

  17. Antineoplastic and Cytotoxic Activities of Nickel(II) Complexes of Thiosemicarbazones

    Hall, Iris H.; Miller, Merrill C.III; West, Douglas X.

    1997-01-01

    Nickel(II) complexes of thiosemicarbazons were observed to be potent cytotoxic agents in human and rodent tissue cultured tumor cells. Each compound demonstrated a slightly different profile in the various histological types of tumors. The nickel complex of Appip demonstrated the most potent in vivo activity in the Ehrlich ascites carcinoma. This agent selectively inhibited L1210 DNA and purine syntheses, and DNA polymerase α, PRPP-amido transferase, IMP-dehydrogenase, dihydrofolate reductase...

  18. Electrochemical and positron annihilation studies of semicarbazones and thiosemicarbazones derived from ferrocene

    A series of six ferrocene derivates containing a semicarbazone or thiosemicarbazone side chain was investigated by cyclic voltammetry and positron annihilation lifetime measurements. Both the redox and the electron capture processes took place on the Fe atom. Correlations between the two methods were proposed. taking into account the substituents on the side chain of the compounds, their redox potentials and the probabilities of o-positronium (o-Ps), formation. (author)

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

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

    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 ...

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

    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

    2011-01-01

    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 diffracti...

  1. α-N-heterocyclic thiosemicarbazone derivatives as potential antitumor agents: A structure-activity relationships approach

    Matesanz, Ana I.; Souza, Pilar

    2009-01-01

    α-N-Heterocyclic thiosemicarbazones, (N)-TSCs, are potent inhibitors of ribonucleotide reductase (RR). This enzyme plays a critical role in DNA synthesis and repair, and is a well-recognized target for cancer chemotherapeutic agents. In this review the structural features of (N)-TSCs, required for maximum antitumour activity have been explored. Special attention is given to the mechanisms of action and structure-activity relationships

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

    Zafer Asım Kaplancıklı; Mehlika Dilek Altıntop; Belgin Sever; Zerrin Cantürk; Ahmet Özdemir

    2016-01-01

    In an effort to develop potent antimicrobial agents, new thiosemicarbazone derivatives were synthesized via the reaction of 4-[4-(trifluoromethyl)phenyl]thiosemicarbazide with aromatic aldehydes. The compounds were evaluated for their inhibitory effects on pathogenic bacteria and yeasts using the CLSI broth microdilution method. Microplate Alamar Blue Assay was also carried out to determine the antimycobacterial activities of the compounds against Mycobacterium tuberculosis H37Rv. Among these...

  3. Complexes of nickel-, copper-, zinc-, cadmium- and mercury (II) with salicyaldehyde-4, 4-dimethyl-3-thiosemicarbazone

    Complexes of salicylaldehyde-4, 4-dimethyl-3-thiosemicarbazone (H2 saldmtsc) with bivalent metal ions of composition [M(saldmtsc).nH2O] (M NiII, CuII, ZnII, CdII or HgII and n=0 or 1), [M(saldmtsc)py] (M=NiII, CuII or ZnII) and [Ni(saldmtsc)B] (B = α-, β- or γ-picoline) have been prepared and characterised. (author)

  4. Intracellular reduction/activation of a disulfide switch in thiosemicarbazone iron chelators

    Akam, Eman A.; Chang, Tsuhen M.; Astashkin, Andrei V.; Tomat, Elisa

    2014-01-01

    Iron scavengers (chelators) offer therapeutic opportunities in anticancer drug design by targeting the increased demand for iron in cancer cells as compared to normal cells. Prochelation approaches are expected to avoid systemic iron depletion as chelators are liberated under specific intracellular conditions. In the strategy described herein, a disulfide linkage is employed as a redox-directed switch within the binding unit of an antiproliferative thiosemicarbazone prochelator, which is acti...

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

    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 o...

  6. Discovery of trypanocidal thiosemicarbazone inhibitors of rhodesain and TbcatB

    Mallari, Jeremy P.; Shelat, Anang; Kosinski, Aaron; Conor R Caffrey; Connelly, Michele; Zhu, Fangyi; McKerrow, James H.; Guy, R. Kiplin

    2008-01-01

    Human African trypanosomiasis (HAT) is caused by the protozoan parasite Trypanosoma brucei. The cysteine proteases of T.brucei have been shown to be crucial for parasite replication and represent an attractive point for therapeutic intervention. Herein we describe the synthesis of a series of thiosemicarbazones and their activity against the trypanosomal cathepsins TbcatB and rhodesain, as well as human cathepsins L and B. The activity of these compounds was determined against cultured T.bruc...

  7. Solvent extraction of cobalt(II) with 2,4-dihydroxyacetophenone thiosemicarbazone

    The extraction of cobalt(II) from ammonium chloride-ammonium hydroxide buffer solutions of pH 6.5 by 2,4-dihydroxyacetophenone thiosemicarbazone (DATS) in n-butanol has been studied. Cobalt(II) forms 1:1 complex (metal:reagent) with DATS. Addition to pyridine enhances the extraction. The influence of metal concentration and the effect of diverse ions on the extraction of cobalt(II) have been investigated. (author)

  8. Investigation of some novel ligands of pyruvaldehyde bis(thiosemicarbazone) as pet radiopharmaceuticals

    Three novel ligands of pyruvaldehyde bis (thiosemicarbazone) have been synthesized. These ligands are labelled with 64Cu. The factors that affect labelling yield are also investigated. The biodistribution of three 64Cu ligand complexes in mice are determined. The higher brain uptake with a prolonged retention time is found in case of 64Cu-PTSP. The results suggested that 62Cu-PTSP may be used as a PET tracer for cerebral perfusion and it needs more research

  9. Solvent extraction of cobalt(II) with 2,4-dihydroxyacetophenone thiosemicarbazone

    Reddy, A.V.; Reddy, M.L.P.; Reddy, Y.K. (Sri Venkateswara Univ., Tirupati (India). Dept. of Chemistry)

    1984-07-19

    The extraction of cobalt(II) from ammonium chloride-ammonium hydroxide buffer solutions of pH 6.5 by 2,4-dihydroxyacetophenone thiosemicarbazone (DATS) in n-butanol has been studied. Cobalt(II) forms 1:1 complex (metal:reagent) with DATS. Addition to pyridine enhances the extraction. The influence of metal concentration and the effect of diverse ions on the extraction of cobalt(II) have been investigated.

  10. Spectroscopic characterization of copper(II) complexes of indoxyl N(4)-methyl thiosemicarbazone

    Chandra, Sulekh; Kumar, Umendra

    2004-10-01

    New copper(II) complexes of indoxyl thiosemicarbazone (ITSC) of general composition CuL 2X 2 (where L: ITSC; X: Cl -, NO 3-, ClO 4-, NCS -) have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibility measurements and spectral (electronic, IR, EPR, 1H NMR , Mass) studies. Cyclic voltammetry measurements show quasi-reversible Cu 2+/Cu 1+ couple. Various physico-chemical techniques suggest a tetragonal structure for these copper(II) complexes.

  11. Novel "hybrid" iron chelators derived from aroylhydrazones and thiosemicarbazones demonstrate selective antiproliferative activity against tumor cells.

    Lovejoy, David B; Richardson, Des R

    2002-07-15

    We previously demonstrated that 2-hydroxy-1-naphthylaldehyde isonicotinoyl hydrazone (311) and other aroylhydrazone chelators possess potent antineoplastic activity because of their ability to bind iron (Fe). From these studies, we identified structural components of the hydrazones that provide antineoplastic activity, namely the salicylaldehyde and 2-hydroxy-1-naphthylaldehyde moieties. A related group of chelators known as the thiosemicarbazones also show pronounced antitumor activity because of their ability to inhibit ribonucleotide reductase. Considering this, we designed a new series of "hybrid ligands" by condensation of the aldehydes described above with a range of thiosemicarbazides. The parent compound of these ligands is 2-hydroxy-1-naphthylaldehyde thiosemicarbazone (NT). Of 8 NT analogues, 3 chelators, namely NT, N4mT (2-hydroxy-1-naphthylaldehyde-4-methyl-3-thiosemicarbazone), and N44mT (2-hydroxy-1-naphthylaldehyde-4,4-dimethyl-3-thiosemicarbazone), showed high antiproliferative activity against SK-N-MC neuroepithelioma cells (50% inhibitory concentration [IC(50)] = 0.5-1.5 microM). Indeed, their activity was significantly (P <.0001) greater than that of desferrioxamine (DFO) (IC(50) = 22 microM). We demonstrate that 311, a 311 analogue (311m), and several NT-series chelators have significantly (P <.001) greater antiproliferative activity against tumor cells than against a range of normal cell types. For example, the IC(50) values of NT and N4mT in SK-N-MC neuroepithelioma cells were 0.5 microM, whereas for fibroblasts the IC(50) values were greater than 25 microM. Further, the effect of one of the most potent chelators (311m) on preventing the growth of bone marrow stem cell cultures was far less than that of doxorubicin and similar to that of cisplatin. These studies support the further development of these chelators as antiproliferative agents. PMID:12091363

  12. Coordination Chemistry of Polyaromatic Thiosemicarbazones 2: Synthesis and Biological Activity of Zinc, Cobalt, and Copper Complexes of 1-(Naphthalene-2-yl)ethanone Thiosemicarbazone

    Marc-Andre LeBlanc; Antonio Gonzalez-Sarrías; Beckford, Floyd A.; P. Canisius Mbarushimana; Seeram, Navindra P.

    2011-01-01

    A novel thiosemicarbazone from 2-acetonaphthone (represented as acnTSC) has been synthesized and its basic coordination chemistry with zinc(II), cobalt(II), and copper(II) explored. The complexes were characterized by elemental analysis and various spectroscopic techniques and are best formulated as [M(acnTSC)2Cl2] with the metal likely in an octahedral environment. The anticancer activity of the complexes was determined against a panel of human colon cancer cells (HCT-116 and Caco-2). The co...

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

    Beckford, Floyd; 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)-...

  14. Bivalent transition metal complexes of coumarin-3-yl thiosemicarbazone derivatives: Spectroscopic, antibacterial activity and thermogravimetric studies

    Refat, Moamen S.; El-Deen, Ibrahim M.; Anwer, Zeinab M.; El-Ghol, Samir

    2009-02-01

    Schiff base complexes of Cu(II), Co(II) and Ni(II) with two coumarin-3-yl thiosemicarbazone derivatives (1E)-1-(1-(2-oxo-2H-chromen-3-yl)ethylidene)thiosemicarbazide (OCET) and (1E)-1-(1-(6-bromo-2-oxo-2H-chromen-3-yl)ethylidene)thiosemicarbazide (BOCET) were synthesized by the reaction of Cu(II), Co(II) and Ni(II) chlorides with each mentioned ligand with molar ratio 1:2 metal-to-ligand. Both ligands and their metal complexes were characterized by different physicochemical methods, elemental analysis, molar conductivity, (UV-vis, Mass, Infrared, 1H NMR spectra) and also thermal analysis (TG and DTG) techniques. The discussion of the outcome data of the prepared complexes indicate that the coumarin-3-yl thiosemicarbazone derivatives ligands behave as a bidentate ligand through both thione sulphur and azomethine nitrogen with 1:2 (metal:ligand) stoichiometry for all complexes. The molar conductance measurements proved that the complexes are electrolytes. The kinetic thermodynamic parameters such as: E∗, Δ H∗, Δ S∗and Δ G∗are calculated from the DTG curves, all complexes are more ordered except Ni(II) complexes. The antibacterial activity of the coumarin-3-yl thiosemicarbazone derivatives and their metal complexes was evaluated against some kinds of Gram positive and Gram negative bacteria.

  15. Investigation of the salicylaldehyde thiosemicarbazone scaffold for inhibition of influenza virus PA endonuclease.

    Rogolino, Dominga; Bacchi, Alessia; De Luca, Laura; Rispoli, Gabriele; Sechi, Mario; Stevaert, Annelies; Naesens, Lieve; Carcelli, Mauro

    2015-10-01

    The influenza virus PA endonuclease is an attractive target for the development of novel anti-influenza virus therapeutics, which are urgently needed because of the emergence of drug-resistant viral strains. Reported PA inhibitors are assumed to chelate the divalent metal ion(s) (Mg²⁺ or Mn²⁺) in the enzyme's catalytic site, which is located in the N-terminal part of PA (PA-Nter). In the present work, a series of salicylaldehyde thiosemicarbazone derivatives have been synthesized and evaluated for their ability to inhibit the PA-Nter catalytic activity. Compounds 1-6 have been evaluated against influenza virus, both in enzymatic assays with influenza virus PA-Nter and in virus yield assays in MDCK cells. In order to establish a structure-activity relationship, the hydrazone analogue of the most active thiosemicarbazone has also been evaluated. Since chelation may represent a mode of action of such class of molecules, we studied the interaction of two of them, one with and one without biological activity versus the PA enzyme, towards Mg²⁺, the ion that is probably involved in the endonuclease activity of the heterotrimeric influenza polymerase complex. The crystal structure of the magnesium complex of the o-vanillin thiosemicarbazone ligand 1 is also described. Moreover, docking studies of PA endonuclease with compounds 1 and 2 were performed, to further analyse the possible mechanism of action of this class of inhibitors. PMID:26323352

  16. Stereochemical trends of metal derivatives of some heterocyclic-2-thiones and thiosemicarbazones

    Tarlok S Lobana

    2000-06-01

    The interaction of heterocyclic thiones/thiosemicarbazones with metals has been the subject of several investigations as these ligands contain chemically active groups, -N(H)-C(=S)- -N=C(-SH)- ,and are useful model compounds for sulphur-containing analogues of purine and pyrimidine bases. Heterocylic-2-thiones bind to metals in several ways and lead to the formation of monomeric or polymeric complexes. For example, the simplest prototype of heterocylic-2-thiones, namely, pyridine-2-thione has several ways of binding, notably, terminal S-bonding and S-bridging (in neutral form), while in anionic form the modes are terminal S-bonding, S-bridging, N,S-chelation, N,S-bridging, N,S-chelation-cum-S-bridging and N,S-bridging-cum-S-bridging. Similarly, thiosemicarbazones bind to metals as S-bonded unidentates or N,S-chelates. In this paper, the chemistry of pyridine-2-thione, its N-oxide, 2-(benzylthio)pyridine-1-oxide thione with metals like iron(II), ruthenium(II), nickel(II), palladium(II), platinum(II), copper(I), copper(II), silver(I) and mercury(II) is briefly described. As regards thiosemicarbazones, focus is only on two compounds, namely organomercury(II) and organothallium(III). A variety of new molecules, well characterised by NMR and X-ray crystallography, is introduced.

  17. In vivo anticancer activity of vanillin, benzophenone and acetophenone thiosemicarbazones on Swiss albino mice

    Sha Md. Shahan Shahriar; Shaikh M Mohsin Ali; Mele Jesmin; Md. Khairul Islam; Sarozit Mondal

    2014-01-01

    Objective: To study the anticancer activities of three schiff bases viz. vanillin thiosemicarbazone, benzophenone thiosemicarbazone and acetophenone thiosemicarbazone against Ehrlich ascites carcinoma (EAC) cells in Swiss albino mice. Methods: Synthesized compounds have administrated into the intraperitoneal cavity of the EAC inoculated mice at two doses. The anticancer activities have studied by monitoring the parameters such as cell growth inhibition, tumor weight measurement, survival time of EAC bearing mice as well as the changes in depleted hematological parameters due to tumorgenesis. All such data have been compared with those of a known standard drug bleomycin at the dose of 0.3 mg/kg (i.p.).Results:It has been found that these bases enhanced life span, reduced average tumor weight and inhibited tumor cell growth of EAC cell bearing mice remarkably. The results were similar in potency to those obtained with bleomycin. It was also found that the depleted hematological parameters (red blood count, white blood count and haemoglobin content) were found to be restored gradually towards normal within few weeks after ceasing the treatment.Conclusions:The compounds can be primarily considered more or less as potent anticancer agents.

  18. Palladium complexes of pyrrole-2-aldehyde thiosemicarbazone: Synthesis, structure and spectral properties

    Piyali Paul; Samaresh Bhattacharya

    2014-09-01

    Reaction of pyrrole-2-aldehyde thiosemicarbazone (abbreviated as H2L, where H2 stands for the two potentially dissociable protons) with [Pd(PPh3)2Cl2] in ethanol in the presence of NEt3 afforded two complexes, [Pd(PPh3)(HLNS)Cl] and [Pd(PPh3)(LNNS)], where the thiosemicarbazone ligand is coordinated to the metal centre respectively as monoanionic N,S-donor (depicted by HLNS) and dianionic N,N,S-donor (depicted by LNNS). Similar reaction with Na2[PdCl4] afforded a bis-complex, [Pd(HLNS)2]. Crystal structures of all the three complexes have been determined.With reference to the structure of the uncoordinated thiosemicarbazone (H2L), the N,S-coordinationmode observed in [Pd(PPh3)(HLNS)Cl] and [Pd(HLNS)2] is associated with a geometrical change around the imine bond.While the N,N,S-mode of binding observed in [Pd(PPh3)(LNNS)] takes place without any such geometrical change. All three complexes display intense absorptions in the visible and ultraviolet regions, which have been analyzed by TDDFT method.

  19. Microwave synthesis of mixed ligand diimine–thiosemicarbazone complexes of ruthenium(ii): biophysical reactivity and cytotoxicity†

    Beckford, Floyd A.; Shaloski, Michael; Leblanc, Gabriel; Thessing, Jeffrey; Lewis-Alleyne, Lesley C.; Holder, Alvin A.; Li, Liya; Seeram, Navindra P.

    2010-01-01

    A novel microwave-assisted synthetic method has been used to synthesise a series of mixed ligand ruthenium(ii) compounds containing diimine as well as bidentate thiosemicarbazone ligands. The compounds contain the diimine 1,10-phenanthroline (phen) or 2,2′-bipyridine (bpy) and the thiosemicarbazone is derived from 9-anthraldehyde. Based on elemental analyses and spectroscopic data, the compounds are best formulated as [(phen)2Ru(thiosemicarbazone)](PF6)2 and [(phen)2Ru(thiosemicarbazone)](PF6)2 where thiosemicarbazone = 9-anthraldehydethiosemicarbazone, 9-anthraldehyde-N(4)-methylthiosemicarbazone, and 9-anthraldehyde-N(4)-ethylthiosemicarbazone. Fluorescence competition studies with ethidium bromide, along with viscometric measurements suggests that the complexes bind calf thymus DNA (CTDNA) relatively strongly via an intercalative mode possibly involving the aromatic rings of the diimine ligands. The complexes show good cytotoxic profiles against MCF-7 and MDA-MB-231 (breast adenocarcinoma) as well as HCT 116 and HT-29 (colorectal carcinoma) cell lines. PMID:20023905

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

    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. PMID:25061691

  1. On the verification of binding modes of p-dimethylaminobenzaldehyde thiosemicarbazone with mercury(II). The solid state studies

    Trzesowska-Kruszynska, Agata

    2014-08-01

    Two coordination compounds of p-dimethylaminobenzaldehyde thiosemicarbazone, fluorescent chemosensor, have been synthesised from the mercury(II) nitrate and mercury(II) chloride, and subsequently characterised by IR spectroscopy, thermal analysis, as well as single crystal X-ray diffraction technique. The inorganic anion has a distinct influence on binding mode of thiosemicarbazone ligand to Hg(II) ion. In both compounds the metal to ligand stoichiometry is 1:2 and the organic ligands coordinate to Hg ion in the neutral thione form, but they differ in a ligand binding mode and the conformation of the ligand. The crystal packing of mercury(II) nitrate complex with thiosemicarbazone is controlled by the mercury chelate ring-phenylene ring π···π stacking interactions.

  2. Inactivation of lambda phage infectivity and lambda deoxyribonucleic acid transfection by N-methyl-isatin beta-thiosemicarbazone-copper complexes.

    Levinson, W; Helling, R

    1976-01-01

    The infectivity of intact lambda phage and transfection by lambda deoxyribonucleic acid were inactivated by exposure to the copper complexes of N-methyl-isatin beta-thiosemicarbazone, thiosemicarbazide, and semicarbazide, but not methyl-isatin. No inactivation was observed when these compounds were used in the absence of copper sulfate. This confirms our previous observation that the activity of N-methyl-isatin beta-thiosemicarbazone is mediated by its thiosemicarbazone moiety and that the presence of copper is required for action. This represents the first time, to our knowledge, that semicarbazide has been found to possess antiviral activity. It is clear that these compounds act directly on deoxyribonucleic acid; whether the compounds also act on proteins has not been determined. PMID:769669

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

    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

  4. Synthesis, Spectral and Thermal Properties of Some Penta-Coordinated Complexes of Oxovanadium(IV) Derived from Thiosemicarbazones of 4-Aminoantipyrine

    Ram K. Agarwal; PRASAD, Surendra; GAHLOT, Neetu

    2004-01-01

    The paper reports the synthesis of crystalline oxovanadium(IV), VO2+, complexes of thiosemicarbazones, i.e. 4[N-(4'-nitrobenzalidene)amino]antipyrine thiosemicarbazone (4'-NO2BAAPTS) and 4[N-(furan-2'-aldimine)amino]antipyrine thiosemicarbazone (FFAAPTS) with general composition VOX2L (X = Cl, Br, I, NO3 or NCS) and VO(ClO4)2(L)H2O (L = 4'-NO2BAAPTS or FFAAPTS). All the complexes were characterized by elemental analyses, molar mass, molar conductance, magnetic susc...

  5. New Thiosemicarbazone and Talinum triangulare Vegetal Extract Formulations with Potential Anti-corrosion Activity [Novas Formulações de Tiossemicarbazonas e Extrato Vegetal de Talinum triangulare com Potencial Atividade Anticorrosão

    Mariana A . de Albuquerque

    2013-06-01

    Full Text Available Corrosion is a process arising out of a chemical action of the environment on a particular material, causing its deterioration. It may occur in metals, concrete, organic polymers, and others. A promising alternative to prevent corrosion is the use of organic inhibitors. The search for new agents or formulations that enable the diminishing of corrosion effects is evidently necessary; therefore, this work evaluated 3 new formulations which contained thiosemicarbazones 4-hydroxy,3-methoxybenzaldehyde-thiosemicarbazone, 4-ethoxybenzaldehyde-thiosemicarbazone and 4-hydroxybenzaldehyde-thiosemicarbazone with the crude extract of Talinum triangulareleaves in ethyl acetate, aiming at the Fe2+ ion chelation for an anticorrosive action. UV-Vis spectroscopy was used to evaluate the formation of Fe2+ ion complexes; also, to determine the respective coordination numbers with the thiosemicarbazones. Results indicated the increase of the thiosemicarbazone anticorrosive action, which had been evaluated by molecular modeling and potentiodynamic polarization, when there were crude extract of T. triangulareleaves in the formulation.

  6. Synthesis and evaluation of copper radiopharmaceuticals with mixed bis(thiosemicarbazone) ligands

    Four 'mixed' bis(thiosemicarbazone) derivatives of pyruvaldehyde were synthesized that incorporate two dissimilar thiosemicarbazone functions. The corresponding [67Cu]copper(II) complexes were prepared and evaluated as possible copper radiopharmaceuticals. The pyruvaldehyde-based mixed bis(thiosemicarbazone) ligands, CH3C[=NNHC(S)NHMe]CH[=NNHC(S)NHEt] (1), CH3C[=NNHC(S)NHMe]CH[=NNHC(S)NEt2] (2), CH3C[=NNHC(S)NHMe]CH[=NNHC(S)-cyclo-N(CH2)5] (3), and CH3C[=NNHC(S)NHMe]CH[=NNHC(S)-cyclo-N(CH2)6] (4), were obtained by reaction of the appropriate thiosemicarbazide derivative with pyruvaldehyde-2-N4-methylthiosemicarbazone (CH3C[=NNHC(S)NHMe]CHO). The 67Cu-labeled copper(II) complexes of ligands 1-4 were prepared and screened in a rat model to assess the potential of each chelate as a 62Cu-radiopharmaceutical for imaging with positron emission tomography. The 67Cu-complexes of ligands 1-4 exhibit significant uptake into the brain and heart 1 min following intravenous administration to rats. For the 67Cu-complexes of ligands 2, 3, and 4, the cerebral and myocardial uptake of 67Cu is two-to-threefold lower at 2 h than at 1 min postinjection, due to significant biological clearance of these 67Cu-chelates. However, the 67Cu-complex of 1 affords cerebral and myocardial uptake and retention comparable to that of [67Cu]Cu-PTSM in this model. Although the kinetics of this new agent appear attractive, ultrafiltration studies using solutions of dog and human serum albumin reveal that the 67Cu-complex of ligand 1, like Cu-PTSM, interacts more strongly with human albumin than dog albumin. Thus, this new agent would appear to offer no advantage over Cu-PTSM as a 62Cu-labeled tracer for evaluation of regional tissue perfusion

  7. 1-Pyrenecarboxaldehyde thiosemicarbazone:A novel fluorescent molecular sensor towards mercury(Ⅱ)ion

    Xue Mei Wang; Hua Yan; Xin Lu Feng; Yong Chen

    2010-01-01

    A novel and simple fluorescent molecular sensor,1-pyrenecarboxaldehyde thiosemicarbazone(Hpytsc),was synthesized.Its higher sensitivity and selectivity to mercury(Ⅱ)ion were studied through absorption and emission channels.The UV-vis spectra show that the increasing mercury(Ⅱ)ion concentrations result in the decreasing absorption intensity.The fluorescence monomer emission of Hpytsc is enhanced upon binding mercury(Ⅱ)ion,which should be due to the 1:1 complex formation between Hpytsc and metal ion.

  8. Complexes of 3dn Metal Ions with Thiosemicarbazones: Synthesis and Antimicrobial Activity

    Tudor Rosu; Aurelian Gulea; Anca Nicolae; Rodica Georgescu

    2007-01-01

    The chelating behavior of the thiosemicarbazone derivatives of 2-hydroxy-8-R-tricyclo[7.3.1.0.2,7]tridecane-13-one (where R = H, CH3, C6H5) towards Co(II), Ni(II) and Cu(II) has been investigated by elemental analysis, molar conductivity measurements, UV-VIS, IR, ESR spectroscopy and thermal studies. It was deduced from the experiments performed that the ligands coordinate to metal ions in different ways – neutral bidentate or mononegative bidentate – depending on the nature of R. A...

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

    Garima Vatsa

    2004-01-01

    Full Text Available The reactions of bis(cyclopentadienyltitanium(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.

  10. Novel rhenium(V) complexes with thiosemicarbazones of pyruvic or phenylglyoxylic acids

    New rhenium(V) complexes with thiosemicarbazones of pyruvic (L') or phenylglyoxylic (L'') acids were synthesized and isolated in solid state in aqueous solutions of concentrated hydrohalic acids. By the method of elementary analysis formation of complexes, featuring the following composition [ReOL'Cl3]·2H2O, [ReOL''2Br]Br2·2H2O, [ReOL'Br2(OH)]·2H2O, [ReOL''2(OH)]Cl·2H2O, [Re2O3L'2Cl4]·2H2O, was ascertained. Solubility of the complexes in organic solvents was determined

  11. Synthesis of New Thiazine and Thiosemicarbazone Derivatives from D-Xylose

    Xiao Ming JI; He Ping SUN; Hai Wei XU; Hong Min LIU

    2006-01-01

    1,2-O-Isopropylidene-5-O-p-toluenesulfonyl-α-D-erythro-pentofuranos-3-ulose 1 was treated with thiourea and aminothiourea to give a D-ribose derivative 2 bearing a 2-amino 1,3-thiazine ring and a thiosemicarbazone derivative 5, respectively. 2 was acylated with Ac2O and propandioic acid to afford two acylation derivatives 3 and 4, respectively. Reduction of 5with NaBH4 in methanol produced a hydrothiosemicarbazone derivative 6. The absolute configuration of 2 was confirmed by X-ray crystallographic analysis. The structures of all products were elucidated by IR, NMR and HRMS spectra.

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

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

  13. Coordination compounds of titanium(4), zirconium and hafnium(4) with acetone thiosemicarbazone

    Adducts of titanium, zirconium and hafnium tetrachlorides with acetone thiosemicarbazone of 1:1 composition are synthesized from ethyl acetate solutions. It is shown on the base of studying infrared spectra that the ligand is coordinated to titanium, zirconium and hafnium bidentately via atoms of sulphur and azomething nitrogen. Heats of ligands and adducts dissolution in 4N- muriatic acid at 298 K are determined by calorimetry. Heats of gaseous ligand addition to the mole of tetrachloride calculated according to Haber cycle on the base of the conducted measurements are localized in the series Ti > Hf > Zr

  14. Dioxouranium (VI) complexes of macrocyclic ligands derived from 2.6-diacetyl pyridine-bis(thiosemicarbazone)

    The dioxouranium(VI) complex of 2.6-diacetylpyridine-bis(thiosemicarbazone), (DAPTC), [UO2(DAPTC) (NO3)2] and its reactions with diketones are described. The complexes so obtained have been characterized on the basis of elemental analyses, electrical conductance and spectral (i.r. and electronic) data. The parent complex reacts with β-diketones to form a complex of the type [UO2(mac)(NO3)2], where mac is a macrocyclic ligand derived by the condensation of DAPTC and a β-diketone. The ligand, DAPTC, acts as a neutral, terdentate ligand having coordination sites at pyridine nitrogen and two azomethine nitrogens. 27 refs

  15. Coordination compounds of titanium (4), zirconium (4) and hafnium (4) with thiosemicarbazone of benzaldehyde

    Adducts of titanium (4), zirconium (4) and hafnium (4) tetrachlorides with thiosemicarbazone of benzaldehyde of the MCl4xLig and MCl4x2Lig composition are extracted from solutions in nonaqueous ethylacetate. On the basis of infrared spectra in the range of 250-4000 cm-1 a conclusion is drawn about participation of azomethine nitrogen and sulfur atoms in coordination with metal. Studied is the behaviour of synthetized adducts and their components in absolute methanol with the help of paper chromatography, measurement of electric conductivity and pH. It is established that adduct decomposition and simultaneous metal tetrachloride solvolysis take place at dissolving in the alcohol

  16. Spectrophotometric Determination of Arsenic in Water Samples by Thiophene-2-Carboxaldehyde Thiosemicarbazone impregnated with alumina

    Md. Faridur Rahman; Aniruddha Chakraborty; Tanmoy Das

    2015-01-01

    Thiophene-2-carboxaldehyde thiosemicarbazone has been successfully applied as an analytical reagent for micro level solid phase spectrophotometric determination of As (III) at pH 3.5. Here it can be seen that arsenic reacts with the new chelating ligand in acidic medium to form the As (III)-tctsc complex. The complex showed maximum absorbance at λ max 281 nm for As (III) ions. The Beer’s law range was 0.1-1.0 mg/L. Job’s method and Mole-ratio method showed that As (III)-ligand ratio in the co...

  17. Study on the Interaction between Isatin-β-Thiosemicarbazone and Calf Thymus DNA by Spectroscopic Techniques

    Pakravan, Parvaneh; Masoudian, Shahla

    2015-01-01

    The interaction between isatin-β-thiosemicarbazone (IBT) and calf thymus DNA (CT-DNA) was investigated in physiological buffer (pH 7.4) using Neutral Red (NR) dye as a spectral probe by UV–Vis absorption and fluorescence spectroscopy, as well as viscosity measurements. The IBT is stabilized by intercalation in the DNA (K [IBT –DNA] = 1.03×105 M−1), and displaces the NR dye from the NR–DNA complex. The binding constants Kf and number of binding sites (n≈1) of IBT with DNA were obtained by fluor...

  18. Discovery of trypanocidal thiosemicarbazone inhibitors of rhodesain and TbcatB

    Mallari, Jeremy P.; Shelat, Anang; Kosinski, Aaron; Caffrey, Conor R.; Connelly, Michele; Zhu, Fangyi; McKerrow, James H.; Guy, R. Kiplin

    2008-01-01

    Human African trypanosomiasis (HAT) is caused by the protozoan parasite Trypanosoma brucei. The cysteine proteases of T.brucei have been shown to be crucial for parasite replication and represent an attractive point for therapeutic intervention. Herein we describe the synthesis of a series of thiosemicarbazones and their activity against the trypanosomal cathepsins TbcatB and rhodesain, as well as human cathepsins L and B. The activity of these compounds was determined against cultured T.brucei, and specificity was assessed with a panel of four mammalian cell lines. PMID:18420405

  19. Solvent extraction of silver(I) with 2,4-dihydroxy-acetophenone thiosemicarbazone

    The solvent extraction of silver(I) is carried out in acetic acid-sodium acetate buffer solution at pH 5.0 by 2,4-dihydroxyacetophenone thiosemicarbazone (DATS). Ethyl acetate was used as a solvent. It is found that single extraction is sufficient to remove silver(I) completely from the aqueous phase. Silver(I) forms 1:1 complex (metal:reagent) with DATS. The effect of diverse ions on the extraction of silver(I) was investigated. (author)

  20. Bis(pyridine-2-carbaldehyde thiosemicarbazone)zinc(II) dinitrate dihydrate

    Jian-Quan Wang; Li-Min Zhang; Lin Cheng

    2010-01-01

    The asymmetric unit of the title compound, [Zn(C7H8N4S)2](NO3)2·2H2O, contains two Zn(pht)2 cations (pht is pyridine-2-carbaldehyde thiosemicarbazone), four nitrate anions and four water molecules. In the cations, each ZnII ion adopts a distorted octahedral coordination geometry, being chelated by two tridentate pht ligands. In the crystal, the cations, anions and water molecules are connected via O—H...O and N—H...O hydrogen bonds into a three-dimensional network.

  1. Crystal structures of crotonaldehyde semicarbazone and crotonaldehyde thiosemicarbazone from X-ray powder diffraction data

    Atef Arfan; Mwaffak Rukiah

    2015-01-01

    Crotonaldehyde semicarbazone {systematic name: (E)-2-[(E)-but-2-en-1-ylidene]hydrazinecarboxamide}, C5H9N3O, (I), and crotonaldehyde thiosemicarbazone {systematic name: (E)-2-[(E)-but-2-en-1-yldene]hydrazinecarbothioamide}, C5H9N3S, (II), show the same E conformation around the imine C=N bond. Compounds (I) and (II) were obtained by the condensation of crotonaldehyde with semicarbazide hydrochloride and thiosemicarbazide, respectively. Each molecule has an intramolecular N—H...N hydrogen bond...

  2. EXTRACTIVE SPECTROPHOTOMETRIC STUDIES OF ACETOPHENONE 2’, 4’-DIHYDROXY THIOSEMICARBAZONE WITH IRON

    P. K. Rana; R. S. Lokhande; S. M. Pitale; S.P. Janwadkar; P. S. Navarkar; D K Yadav

    2012-01-01

    Acetophenone 2’, 4’-Dihydroxy thiosemicarbazone (APDHTS) as a reagent for the extractive spectrophotometric determination of Iron. The reagent APDHTS gave instantaneous and stable violet colour with Iron at pH 5.0. A linear calibration graph over the concentration range 1 ppm to 10 ppm with a 3σ limit of detection of 0.66 ppm was obtained by applying the spectrophotometric method at wavelength 370 nm. The stoichiometry of the complex is established as 1:1 (M: L) by Job’s method of continuous ...

  3. Synthesis, Spectroscopic, and Antimicrobial Studies on Bivalent Zinc and Mercury Complexes of 2-Formylpyridine Thiosemicarbazone

    Yatendra Kumar; Shikha Parmar; Sulekh Chandra

    2009-01-01

    A series of metal complexes of Zn(II) and Hg(II) having the general composition [ M ( L ) 2 ] X 2 [where L = 2-formylpyridine thiosemicarbazone; M = Zn(II) and Hg(II); X = C l − , N O − 3 and 1 / 2 S O 4 2 − ] have been prepared and characterized by elemental chemical analysis, molar conductance, and spectral (IR and mass) studies. The IR spectral data suggests the involvement of sulphur and azomethane nitrogen in coordination to the central metal ion. On the basis of spectral studies, a tetr...

  4. Metal complexes with paramagnetic thiosemicarbazone. [Complexes of Ni,Fe,Zn,Cd,Pd,Pt

    Ovcharenko, V.I.; Larionov, S.V. (AN SSSR, Novosibirsk. Inst. Neorganicheskoj Khimii)

    1981-10-01

    The complexes of Ni(2), Fe(2), Zn(2), Cd(2), Pd(2) and Pt(2) with the stable nitroxyl radical of thiosemicarbazone 4-formyl- 2, 2, 5, 5-tetramethyl-3-imidazoline-1-oxyl of the composition ML/sub 2/ are synthesized. In the basis of the data of physical methods (IR, EPR, electron spectroscopy) a conclusion is made on the way of the ligand coordination. The study of the magnetic properties of the complexes has shown that in the compounds prepared a weak exchange interaction between unpaired electrons of paramagnetic centres takes place.

  5. Solvent extraction of silver(I) with 2,4-dihydroxy-acetophenone thiosemicarbazone

    Reddy, A.V.; Reddy, Y.K. (Sri Venkateswara Univ., Tirupati (India). Dept. of Chemistry); Reddy, G.S. (Sri Venkateswara Univ. Post-Graduate Centre, Cuddapah (India). Dept. of Chemistry)

    1985-03-01

    The solvent extraction of silver(I) is carried out in acetic acid-sodium acetate buffer solution at pH 5.0 by 2,4-dihydroxyacetophenone thiosemicarbazone (DATS). Ethyl acetate was used as a solvent. It is found that single extraction is sufficient to remove silver(I) completely from the aqueous phase. Silver(I) forms 1:1 complex (metal:reagent) with DATS. The effect of diverse ions on the extraction of silver(I) was investigated.

  6. Microwave assisted synthesis, X-ray crystallography and DFT calculations of selected aromatic thiosemicarbazones

    Serda, Maciej; Małecki, Jan G.; Mrozek-Wilczkiewicz, Anna; Musioł, Robert; Polański, Jarosław

    2013-04-01

    Series of four benzaldehyde thiosemicarbazones has been synthesized under microwave irradiation and characterized structurally by means of infrared and NMR spectroscopies and mass spectrometry. Their crystal structures were determined by single crystal X-ray analysis followed by DFT calculations. Partial charges on the molecular surface and dipole moments of the structures were calculated. Crystal structures are stabilized by intramolecular hydrogen bonding and stacking interactions. Studied compounds are interesting as antiproliferative and antifungal agents acting through interactions with iron. Thus presented results may be useful in design new more active or specific structures.

  7. Coordination Chemistry of Polyaromatic Thiosemicarbazones 2: Synthesis and Biological Activity of Zinc, Cobalt, and Copper Complexes of 1-(Naphthalene-2-ylethanone Thiosemicarbazone

    Marc-Andre LeBlanc

    2011-01-01

    Full Text Available A novel thiosemicarbazone from 2-acetonaphthone (represented as acnTSC has been synthesized and its basic coordination chemistry with zinc(II, cobalt(II, and copper(II explored. The complexes were characterized by elemental analysis and various spectroscopic techniques and are best formulated as [M(acnTSC2Cl2] with the metal likely in an octahedral environment. The anticancer activity of the complexes was determined against a panel of human colon cancer cells (HCT-116 and Caco-2. The compounds bind to DNA via an intercalative mode with binding constants of 9.7×104 M-1, 1.8×105 M-1, and 9.5×104 M-1 for the zinc, cobalt, and copper complexes, respectively.

  8. Coordination Chemistry of Polyaromatic Thiosemicarbazones 2: Synthesis and Biological Activity of Zinc, Cobalt, and Copper Complexes of 1-(Naphthalene-2-yl)ethanone Thiosemicarbazone

    LeBlanc, Marc-Andre; Gonzalez-Sarrías, Antonio; Beckford, Floyd A.; Mbarushimana, P. Canisius; Seeram, Navindra P.

    2012-01-01

    A novel thiosemicarbazone from 2-acetonaphthone (represented as acnTSC) has been synthesized and its basic coordination chemistry with zinc(II), cobalt(II), and copper(II) explored. The complexes were characterized by elemental analysis and various spectroscopic techniques and are best formulated as [M(acnTSC)2Cl2] with the metal likely in an octahedral environment. The anticancer activity of the complexes was determined against a panel of human colon cancer cells (HCT-116 and Caco-2). The compounds bind to DNA via an intercalative mode with binding constants of 9.7 × 104 M−1, 1.8 × 105 M−1, and 9.5 × 104 M−1 for the zinc, cobalt, and copper complexes, respectively. PMID:22303515

  9. Synthesis, experimental and theoretical studies on its crystal structure and FT-IR spectrum of new thiosemicarbazone compound E-2-(4-isopropylbenzylidene)thiosemicarbazone

    Khalaji, Aliakbar Dehno; Mehrani, Sepideh; Eigner, Vaclav; Dusek, Michal

    2013-09-01

    The title compound E-2-(4-isopropylbenzylidene)thiosemicarbazone (1) derived from the reaction of 4-isopropylbenzaldehyde and thiosemicarbazide in ethanol solution has been synthesized and characterized by elemental analyses, FT-IR and 1H NMR spectroscopy and single-crystal X-ray diffraction. Its optimized geometry together with the theoretical assignment of the vibrational frequencies of the title compound has been computed by using density functional theory (DFT) method. In the gas phase the four conformers of the title compound were found and it was found that the conformer Sn1 is the most stable one. The title compound crystallizes in the monoclinic space group P21/c with unit cell parameters: a = 14.4054(4), b = 5.6832(10), c = 14.4337(3) Å, β = 93.306(2)°, V = 1179.70(5) Å3 and Z = 4.

  10. Redox activation of Fe(III)-thiosemicarbazones and Fe(III)-bleomycin by thioredoxin reductase: specificity of enzymatic redox centers and analysis of reactive species formation by ESR spin trapping

    Myers, Judith M.; Cheng, Qing; Antholine, William E.; Kalyanaraman, Balaraman; Filipovska, Aleksandra; Arnér, ArnerElias S.J.; Myers, Charles R.

    2013-01-01

    Thiosemicarbazones such as triapine (Tp) and Dp44mT are tridentate iron (Fe) chelators that have well-documented anti-neoplastic activity. While Fe-thiosemicarbazones can undergo redox-cycling to generate reactive species that may have important roles in their cytotoxicity, there is only limited insight into specific cellular agents that can rapidly reduce Fe(III)-thiosemicarbazones and thereby promote their redox activity. Here we report that thioredoxin reductase-1 (TrxR1) and glutathione r...

  11. Preparation and evaluation of copper-67 labeled copper(II) bis(thiosemicarbazone) derivatives as potential blood flow tracers

    A series of bis(thiosemicarbazone) derivatives of diketones and dialdehydes has been synthesized and labelled with copper-67. The biodistributions of these complexes in rats has been determined following femoral vein injection. Brain and heart levels of the complexes were determined at elapsed times of 1 minute, 5 minutes, and 2 hours as a function of % injected dose per organ

  12. Syntheses and spectroscopic studies on zinc(II) and mercury(II) complexes of isatin-3-thiosemicarbazone

    Akinchan, N. T.; Drożdżewski, P. M.; Holzer, W.

    2002-10-01

    Zinc(II) and mercury(II) complexes were prepared by reacting isatin-3-thiosemicarbazone (ISTSCH) with zinc(II) acetate or mercury(II) bromide. The complexes were characterized by IR, Raman, diffuse reflectance, 1H and 13C NMR spectra and elemental analysis. Tetrahedral structures for Zn(ISTSC) 2 and Hg(ISTSCH)Br 2 are suggested.

  13. Microwave-assisted synthesis of new N4-[bi-(4-fluorophenyl)-methyl]-piperazine thiosemicarbazones under solvent-free conditions

    Qing Han Li; Zhi Gang Zhao

    2008-01-01

    Six new N4-[bi-(4-fluorophenyl)-methyl]-piperazine thiosemicarbazones 3a-f have been prepared starting from [bi-(4-fluor-ophenyl)-methyl]-piperazine in solvent-free condition under microwave irradiation with excellent yields. Their structures have been determined by elemental analysis, IR, MS and 1H NMR data.

  14. Crystal structure of copper(I) thiosemicarbazone complex [CuI(PPh.sub.3./sub.)(catsc)

    Shahsavani, E.; Feizi, N.; Eigner, Václav; Dušek, Michal; Khalaji, A.D.

    2015-01-01

    Roč. 56, č. 5 (2015), s. 1003-1007. ISSN 0022-4766 R&D Projects: GA ČR GA15-12653S Institutional support: RVO:68378271 Keywords : copper (I) * thiosemicarbazone * crystal structure * single crystal Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.508, year: 2014

  15. Increased generation of intracellular reactive oxygen species initiates selective cytotoxicity against the MCF-7 cell line resultant from redox active combination therapy using copper-thiosemicarbazone complexes.

    Akladios, Fady N; Andrew, Scott D; Parkinson, Christopher J

    2016-06-01

    The combination of cytotoxic copper-thiosemicarbazone complexes with phenoxazines results in an up to 50-fold enhancement in the cytotoxic potential of the thiosemicarbazone against the MCF-7 human breast adenocarcinoma cell line over the effect attributable to drug additivity-allowing minimization of the more toxic copper-thiosemicarbazone component of the therapy. The combination of a benzophenoxazine with all classes of copper complex examined in this study proved more effective than combinations of the copper complexes with related isoelectronic azines. The combination approach results in rapid elevation of intracellular reactive oxygen levels followed by apoptotic cell death. Normal fibroblasts representative of non-cancerous cells (MRC-5) did not display a similar elevation of reactive oxygen levels when exposed to similar drug levels. The minimization of the copper-thiosemicarbazone component of the therapy results in an enhanced safety profile against normal fibroblasts. PMID:26951232

  16. Anti-Plasmodial Activity of Aroylhydrazone and Thiosemicarbazone Iron Chelators: Effect on Erythrocyte Membrane Integrity, Parasite Development and the Intracellular Labile Iron Pool

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

    2013-01-01

    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-re...

  17. Examination of the Impact of Copper(II) α-(N)-Heterocyclic Thiosemicarbazone Complexes on DNA Topoisomerase IIα.

    Wilson, James T; Jiang, Xiaohua; McGill, Bradley C; Lisic, Edward C; Deweese, Joseph E

    2016-04-18

    Type II DNA topoisomerases resolve topological knots and tangles in DNA that result from routine cellular processes and are effective targets for anticancer therapeutics. To this end, thiosemicarbazones have been identified as having the ability to kill cancer cells from several cell lines. Literature evidence suggests that at least some thiosemicarbazones have an impact on topoisomerase II activity. However, the mechanism is not as clearly defined. Therefore, we set out to analyze the activity of four α-(N)-heterocyclic thiosemicarbazone compounds against topoisomerase IIα. The ligands, acetylpyridine-ethylthiosemicarbazone (APY-ETSC) and acetylpyrazine-methylthiosemicarbazone (APZ-MTSC), and their copper(II) [Cu(II)] complexes [Cu(APY-ETSC)Cl] and [Cu(APZ-MTSC)Cl] were examined for the ability to impact the catalytic cycle of human topoisomerase IIα. Both [Cu(APY-ETSC)Cl] and [Cu(APZ-MTSC)Cl] were more effective at inhibiting DNA relaxation compared with the ligands alone. Further, both [Cu(APY-ETSC)Cl] and [Cu(APZ-MTSC)Cl] increased double-stranded DNA cleavage levels without inhibiting topoisomerase IIα-mediated DNA ligation. The Cu(II) complexes inactivate enzyme activity over time suggesting a critical interaction with the enzyme. Additionally, we found that the Cu(II)-thiosemicarbazone complexes do not significantly impact DNA cleavage by the catalytic core of the enzyme. This evidence is supported by the fact that both [Cu(APY-ETSC)Cl] and [Cu(APZ-MTSC)Cl], and to a lesser extent the ligands, inhibit topoisomerase IIα-mediated ATP hydrolysis. Based upon kinetic analysis, the Cu(II) complexes appear to be noncompetitive inhibitors of the ATPase domain of topoisomerase IIα. Taken together, our results provide evidence that Cu(II) complexes of α-(N)-heterocyclic thiosemicarbazones catalytically inhibit the enzyme through the ATPase domain but also promote double-stranded DNA cleavage by the enzyme. PMID:26982206

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

    Wilfredo Hernández

    2013-01-01

    Full Text Available The palladium(II bis-chelate complexes of the type [Pd(TSC1-52] (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(TSC12] (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(TSC32] (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..

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

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

    2013-01-01

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

  20. Identification of differential anti-neoplastic activity of copper bis(thiosemicarbazones) that is mediated by intracellular reactive oxygen species generation and lysosomal membrane permeabilization.

    Stefani, Christian; Al-Eisawi, Zaynab; Jansson, Patric J; Kalinowski, Danuta S; Richardson, Des R

    2015-11-01

    Bis(thiosemicarbazones) and their copper (Cu) complexes possess unique anti-neoplastic properties. However, their mechanism of action remains unclear. We examined the structure-activity relationships of twelve bis(thiosemicarbazones) to elucidate factors regarding their anti-cancer efficacy. Importantly, the alkyl substitutions at the diimine position of the ligand backbone resulted in two distinct groups, namely, unsubstituted/monosubstituted and disubstituted bis(thiosemicarbazones). This alkyl substitution pattern governed their: (1) Cu(II/I) redox potentials; (2) ability to induce cellular (64)Cu release; (3) lipophilicity; and (4) anti-proliferative activity. The potent anti-cancer Cu complex of the unsubstituted bis(thiosemicarbazone) analog, glyoxal bis(4-methyl-3-thiosemicarbazone) (GTSM), generated intracellular reactive oxygen species (ROS), which was attenuated by Cu sequestration by a non-toxic Cu chelator, tetrathiomolybdate, and the anti-oxidant, N-acetyl-l-cysteine. Fluorescence microscopy suggested that the anti-cancer activity of Cu(GTSM) was due, in part, to lysosomal membrane permeabilization (LMP). For the first time, this investigation highlights the role of ROS and LMP in the anti-cancer activity of bis(thiosemicarbazones). PMID:26335599

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

    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) 2H 2O] (Ln = La(III) or Pr(III); LH 2 = 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 °C using TG, DTG and DTA techniques. All these complexes decompose gradually with the formation of Ln 2O 3 as the end product. The Judd-ofelt intensity parameter, oscillator strength, transition probability, stimulated emission cross section for different transitions of Pr 3+ for 4-phenyl thiosemicarbazones have been calculated.

  2. Mononuclear ruthenium(III) complexes containing chelating thiosemicarbazones: Synthesis, characterization and catalytic property

    Raja, N.; Ramesh, R.

    2010-02-01

    Mononuclear ruthenium(III) complexes of the type [RuX(EPh 3) 2(L)] (E = P or As; X = Cl or Br; L = dibasic terdentate dehydroacetic acid thiosemicarbazones) have been synthesized from the reaction of thiosemicarbazone ligands with ruthenium(III) precursors, [RuX 3(EPh 3) 3] (where E = P, X = Cl; E = As, X = Cl or Br) and [RuBr 3(PPh 3) 2(CH 3OH)] in benzene. The compositions of the complexes have been established by elemental analysis, magnetic susceptibility measurement, FT-IR, UV-vis and EPR spectral data. These complexes are paramagnetic and show intense d-d and charge transfer transitions in dichloromethane. The complexes show rhombic EPR spectra at LNT which are typical of low-spin distorted octahedral ruthenium(III) species. All the complexes are redox active and display an irreversible metal centered redox processes. Complex [RuCl(PPh 3) 2(DHA-PTSC)] ( 5) was used as catalyst for transfer hydrogenation of ketones in the presence of isopropanol/KOH and was found to be the active species.

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

    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. PMID:26349014

  4. Vanadium Complexes with Hydrazone or Thiosemicarbazone Ligands as Potential Anti-Mycobacterium tuberculosis Agents.

    de Souza, Paula C; Maia, Pedro I S; de Barros, Heloisa B; Leite, Clarice Q F; Deflon, Victor M; Pavan, Fernando R

    2015-01-01

    Tuberculosis (TB) is an infectious disease caused mainly by Mycobacterium tuberculosis (MTB) and still an important public health problem worldwide. Some factors like the emergence of multidrug resistant (MDR) and extensively drug-resistant (XDR) strains make urgent the research of new active compounds. Searching for new inorganic compounds against TB, three new dioxovanadium(V) complexes were obtained upon reaction of [VO(acac)2] with hydrazone and thiosemicarbazone ligands derived from di-2-pyridyl ketone. Spectroscopic studies and X-ray crystallography revealed asymmetrically oxo bridged binuclear complexes of the type [{VO(L(1,2))}2(μ-O)2], involving the hydrazone ligands, while a mononuclear square pyramidal complex of the type [VO2(L(3))] was formed with the thiosemicarbazone ligand. The compounds were tested against M. tuberculosis and three of them, with MICs values between 2.00 and 3.76 μM were considered promising for TB treatment. Such MIC values are comparable or better than those found for some drugs currently used in TB treatment. PMID:24433444

  5. Synthesis and biological evaluation of some new N4-aryl substituted 5-chloroisatin-3-thiosemicarbazones.

    Pervez, Humayun; Ramzan, Muhammad; Yaqub, Muhammad; Nasim, Faiz-ul-Hassan; Khan, Khalid Mohammed

    2012-05-01

    A new series of sixteen N4-aryl substituted 5-chloroisatin-3-thiosemicarbazones 2a-2p has been synthesized, characterized and tested for selected biological activities i.e. cytotoxicity, phytotoxicity and urease inhibition. In the brine shrimp bioassay, all the synthesized compounds gave LD50 values>2.30x10(-4) M-2.79x10(-4) M and were, therefore, found to be almost inactive, whereas in phytotoxicity assay, regardless of the nature of aryl substituents, they displayed weak to moderate (5-40%) phytotoxic activity at the highest tested concentrations (500 or 1000 μg/mL). In urease inhibition bioassay, compounds 2a, 2c, 2e, 2f, 2k and 2m exhibited relatively a higher degree of urease inhibition with IC50 values ranging from 38.91 μM to 76.65 μM and thus proved to be potent inhibitors of the enzyme. Of these, 2f and 2m displayed pronounced inhibition with IC50 values 38.91 μM and 39.50 μM, respectively, and may act as lead compounds for further studies. Structure-activity relationship (SAR) studies revealed that electronic effects of the substituents about the phenyl ring at N4 of the thiosemicarbazone moiety played an important role in enhancing the urease inhibitory potential of some of the synthesized compounds. PMID:22530899

  6. The development of radiogallium-acetylacetonate bis(thiosemicarbazone) complex for tumour imaging

    Background: Various radiometal complexes have been developed for tumour imaging, especially Ga-68 tracer. In this work, the development of a radiogallium bis(thiosemicarbazone) complex has been reported. Material and method: [67Ga]acetylacetonate bis(thio-semicarbazone) complex ([67Ga]AATS) was prepared starting with [67Ga]Gallium acetate and freshly prepared acetylacetonate bis(thiosemicarbazone) (AATS) for 30 min at 90oC. The partition co-efficient and stability of the tracer was determined in final solution (25oC) and the presence of human serum (37oC) for up to 24 hours. The biodistribution of the labelled compound in wild-type and fibrosarcoma-bearing rodents were determined for up to 72 hours. Results: The radiolabelled Ga complex was prepared to a high radiochemical purity (> 97%, HPLC) followed by initial biodistribution data with the significant tumour accumulation of the tracer at two hours, which is far higher than free Ga-67 cation, while the compound wash-out is significantly faster. Conclusion: The above-mentioned pharmacokinetic properties suggest an interesting radiogallium complex prepared by the PET Ga radioisotope, 68Ga, in accordance with the physical half life, for use in fibrosarcoma tumours and possibly in other malignancies. (authors)

  7. Thermodynamics of complexation of isatin-3-thiosemicarbazone (HIT and other related derivatives with some metal ions

    H. H. MENA

    2002-04-01

    Full Text Available Proton-ligand formation constants of isatin-3-thiosemicarbazone (HIT ; N-acetylisatin-3-thiosemicarbazone (HAIT and 5-(p-nitrobenzoyl-1,2,4-triazino[5,6-b]indole-3-thione (HBITr ligands and their corresponding metal-ligand formation constants with Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, UO22+ and Th2+ ions were determined pH-metrically at 10, 20, 30 and 40°C in 75 %(v/v ethanol–water. The thermodynamic parameters (DG, DH and DS were also evaluated. It was found that both log K1 and –DH1, for HIT and HAIT-complexes are somewhat larger than log K2and –DH2, indicating a change in the dentate character of these ligands from tridentate (ONN-donors in 1:1 chelates to bidentate (ON-donors in 1:2; M:L chelates. In contrast, the values of log K2 and – DH2 for HBITr-complexes are somewhat larger than log K1 and –DH1, indicating a strong trans-effect for the second coordination. The dissociation process is non-spontaneous, endothermic and entropically unfavourable while the complexation process is spontaneous, exothermic and entropically favourable. The thermodynamic parameters were separated into their electrostatic (el and non-electrostatic (non constituents.

  8. Preparation and evaluation of 61Cu-thiophene-2-aldehyde thiosemicarbazone for PET studies

    Background: [61Cu]Thiophene-2-aldehyde thiosemicarbazone (61CuTATS) was prepared according to an analogy of carrier copper compound with antitumor activity, for eventual use in PET. Material and Methods: [61Cu]TATS was prepared using copper-61 acetate and in-house made ligand (TATS) in one step. 61Cu was produced via the natZn(p,x)61Cu nuclear reaction (180 eA, 22 MeV, 3.2 h) followed by a two-step chromatography method (222 GBq of 61Cu2+). 61Cu TATS preparation was optimized for reaction conditions (buffer concentration and temperature). The tracer was finally administered to normal rats for biodistribution studies. Results: Total radiolabelling of the tracer took 30 minutes with a radiochemical purity of more than 90% (using HPLC and RTLC) and specific activity of about 250-300 Ci/mmol. The complex was stable in the presence of human serum for an hour. The biodistribution of copper cation and the tracer was checked in wild-type rats for up to 2 hours with significant spleen and lung uptake of the tracer. Preparation and evaluation of 61Cu-thiophene-2-aldehyde thiosemicarbazone for PET studies. Conclusion: The production of 61Cu via the natZn(p,x)61Cu is an efficient and reproducible method with high specific activity leading to the production and preliminary evaluation of 61Cu TATS, a potential PET tracer, was reported. (authors)

  9. Synergism and antagonism in Iron base metallic glass corrosion inhibition by Thiosemicarbazone Compounds and Bromide Ions

    The synergistic and antagonism action caused by Br ions on the corrosion inhibition of fe78B13Si19 glassy alloy in 0.2 M Na2SO4 in absence and presence 10 (to power-4) M of some thiosemicarbazone derivatives have been investigated using potentiodynamic polarization, a.c. impedance techniques and morphological study. Results show that the addition of Br ions to sulphate solution inhibit the corrosion process by acting as an electron transfer barrier due to direct adsorption of these ions on alloy surface. A synergistic effect exists when fixed concentration of studied thiosemicarbazone derivatives and low concentration Br ions are used together to prevent glassy alloy corrosion in Na2SO4. The increase in surface coverage values in the presence at low concentrations Br ions indicates that an insoluble complex formed by undergoing a joint adsorption. The synergism parameter (S) is defined and calculated by the surface coverage values. The parameter in the case of small amount of Br found to be more than unity, indicating that the enhanced inhibition efficiency caused by the addition of Br ions is only due to synergism and there is a definite contribution from the inhibitor molecule. (author)

  10. 2-Hydroxy-4-n-butoxy-5-bromoacetophenone thiosemicarbazone as an extractive spectrophotometric reagent for nickel

    K. N. Patel

    2011-05-01

    Full Text Available 2-hydroxy-4-n-butoxy-5-bromoacetophenone thiosemicarbazone (HBBrAT is spectrophotometric reagent for nickel (II in chloroform. The metal ion reacts with 2-hydroxy-4-n-butoxy-5-bromoacetophenone thiosemicarbazone (HBBrAT forming a dark brown coloured complex in the pH range 7.0-11.0. The complex shows maximum absorption at 440 nm. Beer’s law is obeyed in the range 2.74-6.86 µg/mL. The molar absorptivity and Sandell’s sensitivity are found to be 5229 Lmol-1cm-1 and 0.0105 µgcm-2, respectively. The solid complex have been isolated and characterized on the basis of elemental analysis, UV, IR, NMR and Mass spectra. HBBrAT is found to be a selective and strong chelating agent for nickel. The results deduced from Job’s method of continuous variation, the mole ratio and the slope ratio method showed that metal: ligand ratio in the complex to be 1:2. The stability constant of the complex found to be 1.92 X 107. The free energy change for the complex formation reaction is found to be -10.158 K cal/mole at 32 0C. The complex is fairly stable for about 24 h and up to 55 oC.

  11. A novel zinc bis(thiosemicarbazone) complex for live cell imaging.

    Dayal, Disha; Palanimuthu, Duraippandi; Shinde, Sridevi Vijay; Somasundaram, Kumaravel; Samuelson, Ashoka G

    2011-04-01

    Fluorescent zinc complexes have recently attracted a lot of interest owing to their vast applications in cellular imaging. We report the synthesis as well as physical, chemical and biological studies of a novel zinc glyoxalbis(4-methyl-4-phenyl-3-thiosemicarbazone), [Zn(GTSC)]₃, complex. As compared with the well-studied zinc biacetylbis(4-methyl-3-thiosemicarbazone), Zn(ATSM), complex, which was used as a reference, [Zn(GTSC)]₃ had 2.5-fold higher fluorescence. When cellular fluorescence was measured using flow cytometry, we observed that [Zn(GTSC)]₃ had 3.4-fold to 12-fold higher fluorescence than Zn(ATSM) in various cell lines (n = 9) of different tissue origin. Confocal fluorescence microscopy results showed that [Zn(GTSC)]₃ appeared to have a nuclear localization within 30 min of addition to MCF7 cells. Moreover, [Zn(GTSC)]₃ showed minimal cytotoxicity compared with Zn(ATSM), suggesting that [Zn(GTSC)]₃ may be less deleterious to cells when used as an imaging agent. Our data suggest that the novel [Zn(GTSC)]₃ complex can potentially serve as a biocompatible fluorescent imaging agent for live cells. PMID:21384247

  12. Synthesis and Structure-Activity Correlation Studies of Metal Complexes of α-N-heterocyclic Carboxaldehyde Thiosemicarbazones in Shewanella oneidensis

    Quintell Tillison

    2005-04-01

    Full Text Available This investigation involved the synthesis of metal complexes to test the hypothesis that structural changes and metal coordination in pyridine thiosemicarbazones affect cell growth and cell proliferation in vitro. Thiosemicarbazones are well known to possess antitumor, antiviral, antibacterial, antimalarial, and other activities. Extensive research has been carried out on aliphatic, aromatic, heterocyclic and other types of thiosemicarbazones and their metal complexes. Due to the pronounced reactivity exhibited by metal complexes of heterocyclic thiosemicarbazones, synthesis and structural characterization of di-2-pyridylketone 4N-phenyl thiosemicarbazone and diphenyl tin (Sn and platinum (Pt complexes were undertaken. Shewanella oneidensis MR-1, a metal ion-reducing bacterium, was used as a model organism to explore the biological activity under aerobic conditions. A comparision of the cytotoxic potential of selected ligand and metal-complex thiosemicarbazones on cell growth in wild type MR-1 and mutant DSP-010 Shewanella oneidensis strains at various concentrations (0, 5, 10, 15, 20 or 25 ppm was performed. The wild type (MR-1 grown in the presence of increasing concentrations of Sn- thiosemicarbazone complexes was comparatively more sensitive (mean cell number = 4.8 X 108 + 4.3 X 107 SD than the DSP-010, a spontaneous rifampicillin derivative of the parent strain (mean cell number = 5.6 x 108 + 6.4 X 107 SD under comparable aerobic conditions (p=0.0004. No differences were observed in the sensitivity of the wild and mutant types when exposed to various concentrations of diphenyl Pt- thiosemicarbazone complex (p= 0.425 or the thiosemicarbazone ligand (p=0.313. Growth of MR-1 in the presence of diphenyl Sn- thiosemicarbazone was significantly different among treatment groups (p=0.012. MR-1 cell numbers were significantly higher at 5ppm than at 10 to 20ppm (p = 0.05. The mean number of DSP-010 variant strain cells also differed among diphenyl Sn

  13. Synthesis and evaluation of copper radiopharmaceuticals with mixed bis(thiosemicarbazone) ligands

    Ackerman, Lily J.; West, Douglas X.; Mathias, Carla J.; Green, Mark A. E-mail: magreen@pharmacy.purdue.edu

    1999-07-01

    Four 'mixed' bis(thiosemicarbazone) derivatives of pyruvaldehyde were synthesized that incorporate two dissimilar thiosemicarbazone functions. The corresponding [{sup 67}Cu]copper(II) complexes were prepared and evaluated as possible copper radiopharmaceuticals. The pyruvaldehyde-based mixed bis(thiosemicarbazone) ligands, CH{sub 3}C[=NNHC(S)NHMe]CH[=NNHC(S)NHEt] (1), CH{sub 3}C[=NNHC(S)NHMe]CH[=NNHC(S)NEt{sub 2}] (2), CH{sub 3}C[=NNHC(S)NHMe]CH[=NNHC(S)-cyclo-N(CH{sub 2}){sub 5}] (3), and CH{sub 3}C[=NNHC(S)NHMe]CH[=NNHC(S)-cyclo-N(CH{sub 2}){sub 6}] (4), were obtained by reaction of the appropriate thiosemicarbazide derivative with pyruvaldehyde-2-N{sup 4}-methylthiosemicarbazone (CH{sub 3}C[=NNHC(S)NHMe]CHO). The {sup 67}Cu-labeled copper(II) complexes of ligands 1-4 were prepared and screened in a rat model to assess the potential of each chelate as a {sup 62}Cu-radiopharmaceutical for imaging with positron emission tomography. The {sup 67}Cu-complexes of ligands 1-4 exhibit significant uptake into the brain and heart 1 min following intravenous administration to rats. For the {sup 67}Cu-complexes of ligands 2, 3, and 4, the cerebral and myocardial uptake of {sup 67}Cu is two-to-threefold lower at 2 h than at 1 min postinjection, due to significant biological clearance of these {sup 67}Cu-chelates. However, the {sup 67}Cu-complex of 1 affords cerebral and myocardial uptake and retention comparable to that of [{sup 67}Cu]Cu-PTSM in this model. Although the kinetics of this new agent appear attractive, ultrafiltration studies using solutions of dog and human serum albumin reveal that the {sup 67}Cu-complex of ligand 1, like Cu-PTSM, interacts more strongly with human albumin than dog albumin. Thus, this new agent would appear to offer no advantage over Cu-PTSM as a {sup 62}Cu-labeled tracer for evaluation of regional tissue perfusion.

  14. Diphenyllead(IV) chloride complexes with benzilthiosemicarbazones. The first bis(thiosemicarbazone) derivatives.

    Calatayud, David G; López-Torres, Elena; Mendiola, M Antonia

    2007-11-26

    Reactions of diphenyllead(IV) chloride with benzil bis(thiosemicarbazone) (L1H6) and benzil bis(4-methyl-3-thiosemicarbazone) (L1Me2H4) afforded the first complexes containing the diphenyllead(IV) moiety with bis(thiosemicarbazone) ligands. The new complexes show diverse structural characteristics depending on the ligand and the working conditions. Complexes [PbPh2Cl(L1H5)].3H2O (1) and [PbPh2Cl(L1Me2H3)] (3) are mononuclear species in which the ligands are partially deprotonated and the lead atom has a C2N2S2Cl environment in a distorted pentagonal bipyramid coordination geometry. Complex [PbPh(L1Me2H2)](2).2H2O (4) was also obtained, which contains two lead atoms in a binuclear structure with a C2N2S3 coordination sphere for each lead atom, since both dideprotonated ligands act as N2S2 chelate and as sulfur bridge. Reaction from L1H6, in the same conditions in which complex 4 was prepared, gave a mixture of products: the lead (II) complex [Pb(L1H4)]2 (2) and [PbPh3Cl]n. Reactions with the cyclic molecules 5-methoxy-5,6-diphenyl-4,5-dihydro-2H-[1,2,4]-triazine-3-thione (L2H2OCH3) and 5-methoxy-4-methyl-5,6-diphenyl-4,5-dihydro-2H-[1,2,4]-triazine-3-thione (L2MeHOCH3) were also explored. In all the complexes, the ligands are deprotonated. The complexes [PbPh2(L2)2] (5) and [PbPh2(L2MeOCH3)2] (7) present the same characteristics. The X-ray structure of 5 shows a distorted octahedral geometry around the lead atom, with the ligand molecules acting as NS chelates, but the nitrogen bonded to the metal is different; one of the triazines shows a novel behavior, since the nitrogen atom of the new imine group formed is the one that is bonded to the lead center, being a good example of linkage isomerism. The complex [PbPh2Cl(L2)] (6), which was also isolated, could not be crystallized. All the complexes were characterized by elemental analysis, mass spectrometry, IR and 1H, 13C, and 207Pb NMR spectroscopy and some of them by X-ray diffraction studies. PMID:17939655

  15. Iron Chelators of the Di-2-pyridylketone Thiosemicarbazone and 2-Benzoylpyridine Thiosemicarbazone Series Inhibit HIV-1 Transcription: Identification of Novel Cellular Targets—Iron, Cyclin-Dependent Kinase (CDK) 2, and CDK9S⃞

    Debebe, Zufan; Ammosova, Tatyana; Breuer, Denitra; Lovejoy, David B.; Kalinowski, Danuta S.; Karla, Pradeep K.; Kumar, Krishna; Jerebtsova, Marina; Ray, Patricio; Kashanchi, Fatah; Gordeuk, Victor R.; Richardson, Des R.

    2011-01-01

    HIV-1 transcription is activated by HIV-1 Tat protein, which recruits cyclin-dependent kinase 9 (CDK9)/cyclin T1 and other host transcriptional coactivators to the HIV-1 promoter. Tat itself is phosphorylated by CDK2, and inhibition of CDK2 by small interfering RNA, the iron chelator 2-hydroxy-1-naphthylaldehyde isonicotinoyl hydrazone (311), and the iron chelator deferasirox (ICL670) inhibits HIV-1 transcription. Here we have analyzed a group of novel di-2-pyridylketone thiosemicarbazone- and 2-benzoylpyridine thiosemicarbazone-based iron chelators that exhibit marked anticancer activity in vitro and in vivo (Proc Natl Acad Sci USA 103:7670–7675, 2006; J Med Chem 50:3716–3729, 2007). Several of these iron chelators, in particular 2-benzoylpyridine 4-allyl-3-thiosemicarbazone (Bp4aT) and 2-benzoylpyridine 4-ethyl-3-thiosemicarbazone (Bp4eT), inhibited HIV-1 transcription and replication at much lower concentrations than did 311 and ICL670. Neither Bp4aT nor Bp4eT were toxic after a 24-h incubation. However, longer incubations for 48 h or 72 h resulted in cytotoxicity. Analysis of the molecular mechanism of HIV-1 inhibition showed that the novel iron chelators inhibited basal HIV-1 transcription, but not the nuclear factor-κB-dependent transcription or transcription from an HIV-1 promoter with inactivated SP1 sites. The chelators inhibited the activities of CDK2 and CDK9/cyclin T1, suggesting that inhibition of CDK9 may contribute to the inhibition of HIV-1 transcription. Our study suggests the potential usefulness of Bp4aT or Bp4eT in antiretroviral regimens, particularly where resistance to standard treatment occurs. PMID:20956357

  16. Cu, Pt, and Pd complexes of the 3-deoxy-1,2-bis(thiosemicarbazone) derived from D-glucose.

    Horton, D; Varela, O

    2000-09-22

    3-Deoxy-D-erythro-hexos-2-ulose bis(thiosemicarbazone) (1) acts as a tetradentate ligand of the N2S2 type which forms stable coordination complexes with metal(II) cations. The Cu(II), Pt(II), and Pd(II) chelates (2, 4, and 6, respectively) of 1 were synthesized and characterized by elemental analysis and NMR spectroscopy. The NMR spectra of the Pt complex (4) showed the coupling of H-1 and C-1, C-2 of the bis(thiosemicarbazone) with 195Pt (33.7% naturally occurring), which supports the structure proposed for the chelate. The complexes 2, 4, and 6 were acetylated to give the corresponding tri-O-acetyl derivatives 3, 5, and 7. Elimination of Cu(II) from 3 with hydrogen sulfide afforded 8, the tri-O-acetyl derivative of 1. Preliminary studies have shown antiviral activity of chelates 2, 4, and 6 against poliovirus type 1. PMID:11072850

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

    Larsen, Dennis

    The first part of this thesis describes the use of thiosemicarbazones for dynamic combinatorial chemistry. Building blocks incorporating thiosemicarbazides and acetalprotected aldehydes were synthesised and conditions where these building blocks formed dynamic combinatorial libraries under...... of this thesis describes the development of new bifunctional organocatalysts for the formation of hydrazones and oximes at neutral pH. New effective variants of the previously known anthranilic acid-based catalysts were discovered, and via a virtual breakdown of the structure of already identified...... catalysts, two new types of catalysts were discovered: The 2-aminophenols and the 2-(aminomethyl)benzimidazoles. With aldehyde substrates none of the newly discovered catalysts were as effective as a previously discovered benzenephosphonic acid, but with aromatic ketones, an otherwise challenging class of...

  18. Spectroscopic, Thermal and Biological Studies on Some Trivalent Ruthenium and Rhodium NS Chelating Thiosemicarbazone Complexes

    Vinod K. Sharma

    2007-03-01

    Full Text Available The synthetic, spectroscopic, and biological studies of sixteen ring-substituted 4-phenylthiosemicarbazones and 4-nitrophenyl-thiosemicarbazones of anisaldehyde, 4-chlorobenzaldehyde, 4-fluorobenzaldehyde, and vanillin with ruthenium(III and rhodium(III chlorides are reported here. Their structures were determined on the basis of the elemental analyses, spectroscopic data (IR, electronic, H1 and C13 NMR along with magnetic susceptibility measurements, molar conductivity and thermogravimetric analyses. Electrical conductance measurement revealed a 1:3 electrolytic nature of the complexes. The resulting colored products are monomeric in nature. On the basis of the above studies, three ligands were suggested to be coordinated to each metal atom by thione sulphur and azomethine nitrogen to form low-spin octahedral complexes with ruthenium(III while forming diamagnetic complexes with rhodium(III. Both ligands and their complexes have been screened for their bactericidal activities and the results indicate that they exhibit a significant activity.

  19. Platinum and palladium complexes of thiosemicarbazones derived of 2-acetylthiophene: Synthesis and spectral studies

    Neto, J. L.; de Lima, G. M.; Beraldo, H.

    2006-03-01

    The reaction of 2-acetylthiophene thiosemicarbazone (2-HATT) and 2-acetylthiophene 4-phenylthiosemicarbazone (2-HAT-4-FT) with Pd(COD)Cl 2 (COD = 1,5-cyclooctadiene) and trans-Pt 2PEt 3Cl 4 yielded four new metal complexes: [Pd(2-HATT)Cl 2] ( 1), [Pd(2-ATT) 2] ( 2), [Pd(2-AT-4-FT)Cl] ( 3) and [Pt(2-ATT)(PEt 3)Cl] ( 4). Apart from compound 3 all the others were characterised by 1H and 13C{ 1H} NMR, infrared spectroscopy, and elemental analysis. Multinuclear NMR experiments of 31P{ 1H} and 195Pt{ 1H} of complex 4 have revealed that the ligand 2-HATT behaves as a bidentate chelating agent towards Pd(COD)Cl 2 and trans-Pt 2PEt 3Cl 4 whereas ligand 2-HAT-4-FT forms a tridentate chelating complex with Pd(COD)Cl 2.

  20. Synthesis, spectral characterization and eukaryotic DNA degradation of thiosemicarbazones and their platinum(IV) complexes

    Al-Hazmi, G. A.; El-Metwally, N. M.; El-Gammal, O. A.; El-Asmy, A. A.

    2008-01-01

    The condensation products of acetophenone (or its derivatives), salicylaldehyde and o-hydroxy- p-methoxybenzophenone with thiosemicarbazide and ethyl- or phenyl-thiosemicarbazide are the investigated thiosemicarbazones. Their reactions with H 2PtCl 6 produced Pt(IV) complexes characterized by elemental, thermal, mass, IR and electronic spectral studies. The coordination modes were found mononegative bidentate in the acetophenone derivatives and binegative tridentate in the salicylaldehyde derivatives. The complexes were analyzed thermogravimetrically and found highly stable. Some ligands and their complexes were screened against Sarcina sp. and E. coli using the cup-diffusion technique. [Pt( oHAT)(OH)Cl] shows higher activity against E. coli than the other compounds. The degradation power of the tested compounds on the calf thymus DNA supports their selectivity against bacteria and not against the human or related eukaryotic organisms.

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

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

    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 nicke...

  2. Copper complexes of bis(thiosemicarbazones): from chemotherapeutics to diagnostic and therapeutic radiopharmaceuticals.

    Paterson, Brett M; Donnelly, Paul S

    2011-05-01

    The molecules known as bis(thiosemicarbazones) derived from 1,2-diones can act as tetradentate ligands for Cu(II), forming stable, neutral complexes. As a family, these complexes possess fascinating biological activity. This critical review presents an historical perspective of their progression from potential chemotherapeutics through to more recent applications in nuclear medicine. Methods of synthesis are presented followed by studies focusing on their potential application as anti-cancer agents and more recent investigations into their potential as therapeutics for Alzheimer's disease. The Cu(II) complexes are of sufficient stability to be used to coordinate copper radioisotopes for application in diagnostic and therapeutic radiopharmaceuticals. Detailed understanding of the coordination chemistry has allowed careful manipulation of the metal based properties to engineer specific biological activities. Perhaps the most promising complex radiolabelled with copper radioisotopes to date is Cu(II)(atsm), which has progressed to clinical trials in humans (162 references). PMID:21409228

  3. Syntheses and Supramolecular Structures of Two Nickel(Ⅱ) Compounds Based on Two Thiosemicarbazone Ligands

    LI Cheng-juan; FENG Ze-jing; ZHAO Xiao-juan; WANG Su-na; DOU Jian-min

    2013-01-01

    Two new compounds,[Ni2(L1)(Py)6]Py·CH3OH(1) and [Ni3(L2)2(Py)4]·2DMF(2)(H4L1=N,N'-bisalicylbisthiocarbamide; H3L2=3-hydroxyl-2-naphthalene thiosemicarbazide; Py=pyridine; DMF=dimethyl fumarate),based upon two thiosemicarbazone ligands have been obtained and characterized by elemental analysis,Fourier transform infrared(FTIR) and X-ray diffraction(XRD).Compound 1 possesses a binuclear cluster,in which the bisalicylbisthiocarbamide acts as a hexadentate bridge.Compound 2 exhibits a linear trinuclear cluster with the triply-deprotonated ligand acting as pentadentate bridge.C—H…O,C—H…π and C—H…S weak interactions further link these molecules to form interesting supramolecular networks.

  4. Nickel(II) complexes containing thiosemicarbazone and triphenylphosphine: Synthesis, spectroscopy, crystallography and catalytic activity

    Priyarega, S.; Kalaivani, P.; Prabhakaran, R.; Hashimoto, T.; Endo, A.; Natarajan, K.

    2011-09-01

    Four new Ni(II) complexes of the general formula [Ni(PPh 3)(L)] (L = dibasic tridentate ligand derived from 4-diethylamino-salicylaldehyde and thiosemicarbazide or 4-N-substituted thiosemicarbazide) have been reported. The new complexes have been synthesized and characterized by analytical and spectroscopic (IR, electronic, 1H NMR and 31P NMR) techniques. Molecular structure of one of the complexes has been determined by X-ray crystallography. The complex, [Ni(PPh 3)(L4)] (H 2L4 = thiosemicarbazone prepared from 4-diethylamino-salicylaldehyde and 4-phenylthiosemicarbazide) crystallized in monoclinic space group with two molecules per unit cell and has the dimensions of a = 13.232(6) Å, b = 10.181(5) Å, c = 13.574(7) Å, α = 90°, β = 98.483(2)° and γ = 90°. Catalytic activity of the complexes has been explored for aryl-aryl coupling reaction.

  5. Vibrational spectroscopic studies and computational study of ethyl methyl ketone thiosemicarbazone

    Anoop, M. R.; Binil, P. S.; Suma, S.; Sudarsanakumar, M. R.; Y, Sheena Mary.; Varghese, Hema Tresa; Panicker, C. Yohannan

    2010-04-01

    FT-IR and FT-Raman spectra of ethyl methyl ketone thiosemicarbazone were recorded and analyzed. The crystal structure is also described. The vibrational wavenumbers were computed using HF/6-31G(d) and B3LYP/6-31G(d) basis sets and are assigned with the aid of MOLEKEL program. The first hyperpolarizability, infrared intensities and Raman activities are also reported. The calculated first hyperpolarizability is comparable with the reported values of similar derivatives and is an attractive molecule for future applications in non-linear optics. The geometrical parameters of the title compound obtained from XRD studies are in agreement with the calculated values. The red shift of the NH stretching wavenumber in the infrared spectrum compared to the computed wavenumber indicates the weakening of the N-H bond resulting in proton transfer to the neighbouring sulfur atom.

  6. Spectroscopic study one thiosemicarbazone derivative with ctDNA using ethidium bromide as a fluorescence probe.

    Geng, Shaoguang; Wu, Qing; Shi, Lei; Cui, Fengling

    2013-09-01

    In this study, a thiosemicarbazone derivative (E)-2-((1,4-dihydroxy-9,10-anthraquinone-2-yl)methylene)-N-(4-fluorophenyl)hydrazinecarbothioamide (DAFPT) was synthesized, and the interaction of DAFPT with calf thymus DNA (ctDNA) was explored using ethidium bromide (EB) as a fluorescence probe. The binding mode between DAFPT and ctDNA was investigated by UV absorption spectroscopy, fluorescence spectroscopy and molecular docking. The fluorescence quenching mechanism of EB-ctDNA by DAFPT might be a combined quenching type. Thermodynamic parameters showed that the reaction was spontaneous. According to ionic strength, fluorescence polarization and melting temperature (T(m)) curve results, DAFPT-ctDNA interaction was groove binding. The molecular modeling results indicated that DAFPT could slide into the A-T rich region of ctDNA. PMID:23769721

  7. Synthesis and physicochemical study of rhenium(V) complexes with phenylglyoxylic acid thiosemicarbazone

    With high yield (75-93 %) rhenium(V) complexes were prepared with thiosemicarbazone of phenylglyoxylic acid (L) of the composition [ReOLX3]·2H2O, [ReOL2X]X2·2H2O, [ReOLX2(OH)]·2H2O, [ReOL2(OH)]X2 (X = Cl, Br). The compounds prepared were characterized by the methods of elementary and thermal analyses, IR spectroscopy and conductometry. It was ascertained that depending on synthesis conditions, initial concentration of hydrohalic acid first of all, rhenium(V) complexes are formed with different number of ligands in the inner sphere. In all the complexes studied ligand L is coordinated by rhenium atom in bidentate way via sulfur and nitrogen atoms of hydrazine fragment, forming a five-member chelate node

  8. Synthesis, Spectroscopic, and Antimicrobial Studies on Bivalent Zinc and Mercury Complexes of 2-Formylpyridine Thiosemicarbazone

    Sulekh Chandra

    2009-01-01

    Full Text Available A series of metal complexes of Zn(II and Hg(II having the general composition [M(L2]X2 [where L = 2-formylpyridine thiosemicarbazone; M = Zn(II and Hg(II; X = Cl−, NO−3 and 1/2SO42−] have been prepared and characterized by elemental chemical analysis, molar conductance, and spectral (IR and mass studies. The IR spectral data suggests the involvement of sulphur and azomethane nitrogen in coordination to the central metal ion. On the basis of spectral studies, a tetrahedral geometry has been assigned for Zn(II and Hg(II complexes. The free ligand and its metal complexes have been tested in vitro against a number of microorganisms in order to assess their antimicrobial properties.

  9. Coordination compounds of titanium(4), zirconium(4) and hafnium(4) with cyclohexanone thiosemicarbazone

    Adducts of titanium, zirconium and hafnium tetrachlorides with cyclohexanone thiosemicarbazone of 1:1, 1:2, 1:4 composition for zirconium and hafnium, 1:1.5 and 1:4 for titanium were synthesized. Infrared spectra of prepared compounds were studied and an assumption was made concerning the bidentate ligand coordination through sulfur atoms and amino group nitrogen. Solution heats of synthesized adducts in hydrochloric acid were determined and formation heats of adducts and heats of gaseous ligand addition to metal tetrachloride were calculated. It was shown that hafnium formed more stable compounds as compared to zirconium. Ways of coordination of the first, the second, the third and the fourth ligand (L) molecules in MCl4 X 4L compounds were discussed on the basis of infrared spectroscopic and thermochemical investigation

  10. Synthesis, Spectroscopic, and Antimicrobial Studies on Bivalent Zinc and Mercury Complexes of 2-Formylpyridine Thiosemicarbazone

    Chandra, Sulekh; Parmar, Shikha; Kumar, Yatendra

    2009-01-01

    A series of metal complexes of Zn(II) and Hg(II) having the general composition [M(L)2]X2 [where L = 2-formylpyridine thiosemicarbazone; M = Zn(II) and Hg(II); X = Cl−, NO3− and 1/2SO42−] have been prepared and characterized by elemental chemical analysis, molar conductance, and spectral (IR and mass) studies. The IR spectral data suggests the involvement of sulphur and azomethane nitrogen in coordination to the central metal ion. On the basis of spectral studies, a tetrahedral geometry has been assigned for Zn(II) and Hg(II) complexes. The free ligand and its metal complexes have been tested in vitro against a number of microorganisms in order to assess their antimicrobial properties. PMID:19421419

  11. Tin(II) Selective PVC Membrane Electrode Based on Salicylaldehyde Thiosemicarbazone as an Ionophore

    Sulekh Chandra; Kusum Sharma; Adarsh Kumar

    2013-01-01

    A polymeric membrane-based tin selective electrode was developed by using salicylaldehyde thiosemicarbazone (STSC). The best performance was recorded with a membrane composition of PVC : TBP : ionophore : NaTPB as 28 : 59 : 8 : 5 (w/w%). The Nernstian slope calculated from the calibration curve for Sn2+ sensor was 28.8 ± 0.4 mV/decade. The detection limit of the sensor was 2.10 × 10−8 M, in the linear concentration range of 1.0 × 10−2−1.1 × 10−7 M. It was relatively fast response time (...

  12. Synthesis and Biochemical Evaluation of Thiochromanone Thiosemicarbazone Analogues as Inhibitors of Cathepsin L

    2012-01-01

    A series of 36 thiosemicarbazone analogues containing the thiochromanone molecular scaffold functionalized primarily at the C-6 position were prepared by chemical synthesis and evaluated as inhibitors of cathepsins L and B. The most promising inhibitors from this group are selective for cathepsin L and demonstrate IC50 values in the low nanomolar range. In nearly all cases, the thiochromanone sulfide analogues show superior inhibition of cathepsin L as compared to their corresponding thiochromanone sulfone derivatives. Without exception, the compounds evaluated were inactive (IC50 > 10000 nM) against cathepsin B. The most potent inhibitor (IC50 = 46 nM) of cathepsin L proved to be the 6,7-difluoro analogue 4. This small library of compounds significantly expands the structure–activity relationship known for small molecule, nonpeptidic inhibitors of cathepsin L. PMID:24900494

  13. Synthesis and spectral studies of platinum metal complexes of benzoin thiosemicarbazone

    Offiong, Offiong E.

    1994-11-01

    The platinum metal chelates of benzoin thiosemicarbazone obtained with Ru(III), Rh(III), Ir(III), Pd(II) and Pt(II) were prepared from their corresponding halide salts. The complexes were characterized by elemental analysis, conductance measurement, IR, Raman, 1H-NMR, 13C-NMR and UV-visible spectra studies. Various ligand field parameters and nephelauxetic parameters were also calculated. The mode of bonding and the geometry of the ligand environment around the metal ion have been discussed in the light of the available data obtained. Complexes of Ru(III), Rh(III) and Ir(III) are six-coordinate octahedral, while Pd(II) and Pt(II) halide complexes are four-coordinated with halides bridging.

  14. Dioxouranium (VI) complexes of macrocyclic ligands derived from 2. 6-diacetyl pyridine-bis(thiosemicarbazone)

    Yadav, H.D.S.; Sengupta, S.K.; Tripathi, S.C.

    The dioxouranium(VI) complex of 2.6-diacetylpyridine-bis(thiosemicarbazone), (DAPTC), (UO/sub 2/(DAPTC) (NO/sub 3/)/sub 2/) and its reactions with diketones are described. The complexes so obtained have been characterized on the basis of elemental analyses, electrical conductance and spectral (i.r. and electronic) data. The parent complex reacts with ..beta..-diketones to form a complex of the type (UO/sub 2/(mac)(NO/sub 3/)/sub 2/), where mac is a macrocyclic ligand derived by the condensation of DAPTC and a ..beta..-diketone. The ligand, DAPTC, acts as a neutral, terdentate ligand having coordination sites at pyridine nitrogen and two azomethine nitrogens. 27 refs.

  15. Comparative analysis of the cytotoxicity of substituted (phenylglyoxal bis(4-methyl-3-thiosemicarbazone)) copper (II) chelates.

    Coats, E A; Milstein, S R; Holbein, G; McDonald, J; Reed, R; Petering, H G

    1976-01-01

    Seven para-substituted [phenylglyoxal bis(4-methyl-3-thiosemicarbazone)]copper (II) chelates (12-18) have been designed, synthesized, and tested for their ability to inhibit the respiration of rat liver slices as a normal cell model and Ehrlich ascites cells as a tumor cell model. Relationships between chemical structure and respiratory inhibition are described on a quantitative basis using substituent contants (pi, Es, and sigmap) by computerized multiparameter regression analyses. The correlations indicate that changes in Es have the largest effect on liver slice toxicity of chelates while pi and sigmap account for most of the variation in toxicity to ascites cells. A comparative analysis strongly suggests that electron-donating substituents with greater water solubility should increase cytotoxicity to ascites cells at the expense of cytotoxicity to the rat liver cells. The predictions of the equations were checked by synthesizing and testing an additional derivative. The results strengthen the initial predictions. PMID:1246035

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

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

    New derivatives of thiosemicarbazone Schiff base with isatin moiety were synthesized L1-L6. The structures of these compounds were characterized based on the spectroscopic techniques. Compound L6 was further characterized by XRD single crystal. The interaction of these compounds with calf thymus (CT-DNA) exhibited high intrinsic binding constant (kb = 5.03-33.00 × 105 M-1) for L1-L3 and L5 and (6.14-9.47 × 104 M-1) for L4 and L6 which reflect intercalative activity of these compounds toward CT-DNA. This result was also confirmed by the viscosity data. The electrophoresis studies reveal the higher cleavage activity of L1-L3 than L4-L6. The in vitro anti-proliferative activity of these compounds against human colon cancer cell line (HCT 116) revealed that the synthesized compounds (L3, L6 and L2) exhibited good anticancer potency.

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

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

    2014-11-01

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

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

    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. PMID:26275470

  19. Synthesis and crystal structure of [chlorobis(triphenylphospino) (p-chlorobenzaldehyde thiosemicarbazone)] copper(I) complex

    Ashiq Khan; Poonam Sharma; Rajnikant; Vivek K Gupta; Naresh Padha; Rekha Sharma

    2016-02-01

    Reactions of copper(I) halides with p-chlorobenzaldehyde thiosemicarbazone (H1L) and triphenylphosphine in 1 : 1 : 2 molar ratio yielded complexes of stoichiometry, [CuX(1-S- H1L)(Ph3P)2] (X = I, 1: Br, 2; Cl, 3). All the three complexes were characterized using analytical (CHNS) and spectroscopic (IR, 1H NMR) techniques. The structure of complex 3 was confirmed by X-ray crystallography. It has been found to crystallize in the triclinic system with space group P-1 and unit cell parameters: a = 10.207(5) Å, b = 13.027(5) Å, c = 16.269(5) Å, = 100.054(5)°, = 99.228(5)° and = 97.234(5)°. This complex has distorted tetrahedral geometry with two phosphorus atoms from two triphenylphosphine ligands, thione sulfur of thiosemicarbazone ligand and chloride ion occupying the four corners of the tetrahedron. The structure of complex 3 was in contrast to sulfur-bridged dinuclear complex of copper(I) chloride with benzaldehydethiosemicarbazone, [Cu2Cl2(2-S-Hbtsc)2(Ph3P)2]·2H2O. The intermolecular H-bonding, Cl· · ·HCph, 2.733 Å and interactions, {CHph · · · , 2.796; 2.776 Å} in this complex led to the formation of 1D chain. Two such 1D chains were cross-linked via, Cl· · ·HCph, 2.896 Å H-bonding to form a 2D network.

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

    A conformationally rigid half-sandwich organoruthenium (II) complex [(η6-p-cymene)RuClTSCN–S]Cl, (1) and carbonyl complex [Ru(CO)Cl(PPh3)2TSCN–S] (2) have been synthesized from the reaction of [{(η6-p-cymene)RuCl}2(μ-Cl)2] and [Ru(H)(Cl)(CO)(PPh3)3] with thiophene-2-carboxaldehyde thiosemicarbazon (TSC) respectively and both novel ruthenium (II) complexes have been characterized by elemental analysis, FT-IR and NMR spectroscopy. The peripheral TSC in the complexes acts as an electrochemical coupling unit providing the ability to carry out electrochemical deposition (ED) and to form an electro-deposited film on a graphite electrode surface. The biosensing applicability of complexes 1 and 2 was investigated by using glucose oxidase (GOx) as a model enzyme. Electrochemical measurements at − 0.9 V versus Ag/AgCl electrode by following the ED Ru(II) reduction/oxidation due to from the enzyme activity, in the presence of glucose substrate. The designed biosensor showed a very good linearity for 0.01–0.5 mM glucose. The in vitro antimicrobial activities of complexes 1 and 2 were also investigated against nine bacterial strains and one fungus by the disc diffusion test method. No activity was observed against the Gram-negative strains and fungus, whereas complex 1 showed moderate antibacterial activities against Gram-positive bacterial strains. - Highlights: • Novel Ru (II) thiosemicarbazone complexes were synthesized and characterized. • Electrochemical depositions were performed. • Rigid half-sandwich Ru (II) complex showed enhanced antibacterial activity

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

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

    2013-02-15

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

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

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

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

    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. PMID:27191616

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

    The extraction behaviour of Th(IV) from aqueous nitric acid medium employing 2-hydroxy-1-naphthaldehyde thiosemicarbazone has been studied in the presence of various donors, like trioctyl phosphine oxide (TOPO), calix[3]OH[3]OMe[6]arene, trioctyl amine (TOA), dimethyl sulphoxide (DMSO) in ethylacetate solvent. The constants (log kex) for the binary complex in organic phase [Th(A)(NO3)3], where A is the ligand, was found to be 3.99, which was by far the largest amongst the corresponding values known for the other thiosemicarbazones. The overall equilibrium constants (log K) for the ternary species [Th(A)TOPO(NO3)3], [Th(A)TOA(NO3)3], [Th(A)Calix[3]OH[3]OMe[6]arene(NO3)3], [Th(A)DMSO(NO3)3] were estimated to be 8.287, 8.862, 8.415, 6.921 respectively. The trend in equilibrium constants were in accordance with the substitution of the donor. The extraction of Th4+ by the ligand-donor combination was maximum at pH = 1 and extraction decreases with increase in pH. It has been found that the extent of extraction of Th4+ in the organic phase as the binary as well as ternary complex [Th(A)(NO3)3] and [Th(A)(NO3)3S], where S is the donor, increases with increase in the concentration of the ligand. Similar trend is obtained in the extraction by donors in absence of ligand. In case of ternary extraction, using different donors, amines are found to perform best compared to the other donors. The trend is as follows: TOA > calix[3]OH[3]OMe[6]arene > TOPO > DMSO. In addition, the effect of different diluents on extraction was also studied and the observed trend was methyl salicylate > ethyl acetate > methyl isobutyl ketone > ethyl benzoate. (orig.)

  5. Interaction of Triapine and related thiosemicarbazones with iron(III)/(II) and gallium(III): a comparative solution equilibrium study†

    Enyedy, Éva A.; Primik, Michael F.; Kowol, Christian R.; Arion, Vladimir B.; Kiss, Tamás; Keppler, Bernhard K.

    2011-01-01

    Stoichiometry and stability of GaIII, FeIII, FeII complexes of Triapine and five related α-N heterocyclic thiosemicarbazones with potential antitumor activity have been determined by pH-potentiometry, UV-vis spectrophotometry, 1H NMR spectroscopy, and spectrofluorimetry in aqueous solution (with 30% DMSO), together with the characterization of the proton dissociation processes. Additionally, the redox properties of the iron complexes were studied by cyclic voltammetry at various pH values. Fo...

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

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

    2005-11-15

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

  7. Spectroscopic, thermal and antibacterial studies on Mn(II) and Co(II) complexes derived from thiosemicarbazone

    SULEKH CHANDRA; MONIKA TYAGI; Moamen S. Refat

    2009-01-01

    Mn(II) and Co(II) complexes having the general composition [M(L)2X2] (where L = 2-pyridinecarboxaldehyde thiosemicarbazone, M = Mn(II) and Co(II), X = Cl- and NO3-) were synthesized. All the metal complexes were characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, EPR, electronic spectral studies and thermogravimetric analysis (TG). Based on the spectral studies, an octahedral geometry was assigned for all the complexes. Thermal studies of th...

  8. Spectroscopic, Viscositic and Molecular Modeling Studies on the Interaction of 3′-Azido-Daunorubicin Thiosemicarbazone with DNA

    Cui, Fengling; Liu, Qingfeng; Luo, Hongxia; Zhang, Guisheng

    2013-01-01

    A new daunorubicin has been synthesized and structurally characterized. The interaction of native calf thymus DNA (ctDNA) with 3′-azido-daunorubicin thiosemicarbazone (ADNRT) was investigated under simulated physiological conditions by multi-spectroscopic techniques, viscometric measurements and molecular modeling study. It concluded that ADNRT could intercalate into the base pairs of ctDNA, and the fluorescence quenching by ctDNA was static quenching type. Thermodynamic parameters calculated...

  9. Cell death and ultrastructural alterations in Leishmania amazonensis caused by new compound 4-Nitrobenzaldehyde thiosemicarbazone derived from S-limonene

    Britta, Elizandra Aparecida; Scariot, Débora Botura; Falzirolli, Hugo; Ueda-Nakamura, Tânia; Silva, Cleuza Conceição; Filho, Benedito Prado Dias; Borsali, Redouane; Nakamura, Celso Vataru

    2014-01-01

    Background The treatment of leishmaniasis with pentavalent antimonials is problematic because of their toxicity. Investigations of potentially active molecules are important to discover less toxic drugs that are viable economic alternatives for the treatment of leishmaniasis. Thiosemicarbazones are a group of molecules that are known for their wide versatility and biological activity. In the present study, we examined the antileishmania activity, mechanism of action, and biochemical alteratio...

  10. Bp44mT: an orally active iron chelator of the thiosemicarbazone class with potent anti-tumour efficacy

    Yu, Y; Rahmanto, Y Suryo; Richardson, DR

    2012-01-01

    BACKGROUND AND PURPOSE Our previous studies demonstrated that a thiosemicarbazone iron chelator (di-2-pyridylketone-4,4-dimethyl-3-thiosemicarbazone; Dp44mT) possesses potent and selective anti-cancer activity but led to cardiotoxicity at non-optimal doses. In this study, we examined the in vivo anti-tumour efficacy and tolerability of a new-generation 2-benzoylpyridine thiosemicarbazone iron chelator (2-benzoylpyridine-4,4-dimethyl-3-thiosemicarbazone; Bp44mT) administered via the oral or i.v. routes. EXPERIMENTAL APPROACH BpT chelators were tested in vitro against human lung cancer cells (DMS-53) and in vivo in DMS-53 tumour xenografts in mice. The toxicity of Bp44mT in vivo and its effects on the expression of iron-regulated molecules involved in growth and cell cycle control were investigated. KEY RESULTS Administration of Bp44mT by either route resulted in marked dose-dependent inhibition of tumour growth. When administered at 50 mg·kg−1 via oral gavage three times per week for 23 days, the net xenograft growth was inhibited by 75%, compared with vehicle-treated mice. Toxicological examination showed reversible alterations including slight reduction of RBC count, with a decrease of liver and splenic iron levels, which confirmed iron chelation in vivo. Importantly, in contrast to Dp44mT, the chelator-treated mice did not show cardiac histological abnormalities. There was also no significant weight loss in mice, suggesting oral administration of Bp44mT was well tolerated. CONCLUSIONS AND IMPLICATIONS This is the first study to show that Bp44mT can be given orally with potent anti-tumour efficacy. Oral administration of a novel and effective chemotherapeutic agent provides the benefits of convenience for chronic dosing regimens. PMID:21658021

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

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

    2014-03-01

    The oxidation of oxyhemoglobin to methemoglobin has been found to be facilitated by low molecular weight iron(III) thiosemicarbazone complexes. This deleterious reaction, which produces hemoglobin protein units unable to bind dioxygen and occurs during the administration of iron chelators such as the well-known 3-aminopyridine-2-pyridinecarbaldehyde thiosemicarbazone (3-AP; Triapine), has been observed in the reaction with Fe(III) complexes of some members of the 3-AP structurally-related thiosemicarbazone ligands derived from di-2-pyridyl ketone (HDpxxT series). We have studied the kinetics of this oxidation reaction in vitro using human hemoglobin and found that the reaction proceeds with two distinct time-resolved steps. These have been associated with sequential oxidation of the two different oxyheme cofactors in the α and β protein chains. Unexpected steric and hydrogen-bonding effects on the Fe(III) complexes appear to be the responsible for the observed differences in the reaction rate across the series of HDpxxT ligand complexes used in this study. PMID:24317633

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

    The Co(II) complexes derived from salicylaldehyde 4-phenyl thiosemicarbazone; SaOHtsc, p-chlorobenzaldehyde 4-phenyl thiosemicarbazone; ph-HClbtsc is reported and characterized based on elemental analysis, IR, magnetic susceptibility measurement, 1H and 13C NMR spectra. The Co(II) complexes have the molecular formula CoL2 where the ligand corresponding to SaOHtsc and ph-HClbtsc. The elemental analysis for the ligands and complexes were in a good agreement with the theoretical values. The ligands coordinate to metal ions in different ways which is through mono negative bidentate or di negative tridentate. The magnetic susceptibility measurements showed that the CoL2 complexes with ligand SaOHtsc are diamagnetic thus making this complexes suitable for NMR studies. The signals at the 10.04 ppm were assigned to N2H in the 1H-NMR spectra of the free ligands was absent in the spectra of the complexes due to the deprotonation of the N2H and coordination to the metal centres. The absence of the band in IR spectrum which is assigned to v(N2-H) in the spectra of CoL2 complexes is due to the deprotonation of the ligands upon complexation through azomethine nitrogen and thionic sulphur atom to metal ion. The thiosemicarbazones and its Co(II) complexes showed moderate inhibitory against bacteria Bacillus Subtilis, Staphylococcus Epidermis, Escherichia Coli and Proteus Mirabilis in 10 μg/ disc. (author)

  13. Preparation and Biodistribution Studies of a Radiogallium-Acetylacetonate Bis (Thiosemicarbazone) Complex in Tumor-Bearing Rodents

    Jalilian, Amir Reza; Yousefnia, Hassan; Shafaii, Kamaleddin; Novinrouz, Aytak; Rajamand, Amir Abbas

    2012-01-01

    Various radiometal complexes have been developed for tumor imaging, especially Ga-68 tracer. In the present study, the development of a radiogallium bis-thiosemicarbazone complex has been reported. [67Ga] acetylacetonate bis(thiosemicarbazone) complex ([67Ga] AATS) was prepared starting [67Ga]Gallium acetate and freshly prepared acetylacetonate bis (thiosemicarbazone) (AATS) in 30 min at 90°C. The partition co-efficient and the stability of the tracer were determined in final solution (25°C) and the presence of human serum (37°C) up to 24 h. The biodistribution of the labeled compound in wild-type and fibrosarcoma-bearing rodents were determined up to 72 h. The radiolabled Ga complex was prepared in high radiochemical purity (> 97%, HPLC) followed by initial biodistribution data with the significant tumor accumulation of the tracer in 2 h which is far higher than free Ga-67 cation while the compound wash-out is significantly faster. Above-mentioned pharmacokinetic properties suggest an interesting radiogallium complex while prepared by the PET Ga radioisotope, 68Ga, in accordance with the physical half life, for use in fibrosarcoma tumors, and possibly other malignancies. PMID:24250475

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

    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

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

    Maia Cabrera

    Full Text Available 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.

  16. Synthesis, characterization, electrochemical studies, and in vitro antibacterial activity of novel thiosemicarbazone and its Cu(II), Ni(II), and Co(II) complexes.

    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, (1)H, (13)C-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

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

    Salman A. Khan

    2014-01-01

    Full Text Available Metal complexes were prepared by the reaction of thiosemicarbazone with CuCl2, NiCl2, CoCl2, Cu(OAc2, Ni(OAc2, and Co(OAc2. 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.

  18. Synthesis, Spectroscopic and Physicochemical Characterization and Biological Activity of Co(II) and Ni(II) Coordination Compounds with 4-Aminoantipyrine Thiosemicarbazone

    Ram K. Agarwal; Surendra Prasad

    2004-01-01

    We describe the synthesis and characterization of cobalt(II) and nickel(II) coordination compounds of 4[N-(furan-2’-aldimine)amino]antipyrine thiosemicarbazone (FFAAPTS) and 4[N-(4'-nitrobenzalidene) amino]antipyrine thiosemicarbazone (4'-NO2BAAPTS). All the isolated compounds have the general composition MX2(L)(H2O) (M = Co2+ or Ni2+; X = Cl, Br, NO3, NCS or CH3COO; L = FFAAPTS or 4'-NO2BAAPTS) and M(ClO4)2(L)2 (M = Co2+ or Ni2+; L = FFAAPTS or 4'-NO2BAAPTS). Infrared spectral studies i...

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

    Pahontu, Elena; Fala, Valeriu; Aurelian GULEA; POIRIER, DONALD; Tapcov, Victor; Rosu, Tudor

    2013-01-01

    Thirty two new Cu(II), Ni(II) and Zn(II) complexes (1–32) with salicylidene thiosemicarbazones (H2L1–H2L10) were synthesized. Salicylidene thiosemicarbazones, of general formula (X)N-NH-C(S)-NH(Y), were prepared through the condensation reaction of 2-hydroxybenzaldehyde and its derivatives (X) with thiosemicarbazide or 4-phenylthiosemicarbazide (Y = H, C6H5). The characterization of the new formed compounds was done by 1H-NMR, 13C-NMR, IR spectroscopy, elemental analysis, magnetochemical, the...

  20. The anticancer thiosemicarbazones Dp44mT and triapine lack inhibitory effects as catalytic inhibitors or poisons of DNA topoisomerase IIα

    Yalowich, Jack C.; Wu, Xing; Zhang, Rui; Kanagasabai, Ragu; Hornbaker, Marissa; Hasinoff, Brian B

    2012-01-01

    The thiosemicarbazones Dp44mT (di-2-pyridylketone-4,4-dimethyl-3-thiosemicarbazone) and triapine have potent antiproliferative activity and have been evaluated as anticancer agents. While these compounds strongly bind iron and copper, their mechanism(s) of action are incompletely understood. A recent report (Rao et al., Cancer Research 69:948-957, 2009) suggested that Dp44mT may, in part, exert its cytotoxicity through poisoning of DNA topoisomerase IIα. In the present report, a variety of as...

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

    Arumugam Manimaran; Chinnasamy Jayabalakrishnan

    2012-01-01

    New hexa-coordinated binuclear Ru(II) thiosemicarbazone complexes of the type {[(B)(EPh3)(CO)ClRu]2L} (where, E = P or As; B = PPh3 or AsPh3 or pyridine; L = mononucleating NS donor of N-substituted thiosemicarbazones) have been synthesized and characterized by elemental analysis, FT-IR, UV–vis and 31P{1H} NMR cyclic voltammetric studies. The DNA-binding studies of Ru(II) complexes with calf thymus DNA (CT-DNA) were investigated by UV–vis, viscosity measurements, gel-electrophoresis and fluor...

  2. 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

    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 com...

  3. Synthesis, characterization and x-ray crystal structure of a dimethyltin (IV) dichloride complex of 2-acetylpyridine benzophenone azine

    Dimethyltin dichloride react with 2-ac ethylpyridine benzophenone azine (apba) in refluxing dry hexane to give (SnMe2 Cl2 (apba)) where the azine ligand acts as a bidentate N-N chelating ligand. The complex has been characterized by IR spectroscopy, 1H and 13C NMR spectroscopic data and elemental analyses. The crystal structure of the dimethyltin(IV) derivative has also been determined. Crystals are monoclinic with space group P2(1)/n with cell dimensions: a = 10.1819(3) Armstrong, b = 18.3113(5) Armstrong, c = 12.6451(4) Armstrong

  4. Cobalt substituted thiosemicarbazone metal complex induced apoptosis in cancer cells via activation of mitochondrial pathway

    Thiosemicarbazone (TSC) and their transition metal complexes are broad class of biologically active small molecules and present a great variety of biological activity ranging from antitumour, fungicide, bacteriocide, anti inflammatory and antiviral activities. These characteristics render the whole class of compounds very interesting. In the present study, we sought to examine cytotoxic activity of thiosemicarbazone cobalt complex on various cancer cell lines along with the possible mechanism through which the compound induce apoptosis in these cell lines. Cytotoxicity of TSC cobalt complex was studied by performing standard MTT drug sensitivity assay and determining its IC50 value on various leukemic and solid cancer cell lines like HL-60, MOLT-4, K-562 and COLO-205. Cellular damage upon the treatment of test molecule was analyzed by conducting LDH release assay. DNA fragmentation and morphology of apoptotic cells were assessed respectively by performing ladder assay and acridine orange/ethidium bromide staining. Role of mitochondria in the induction of cell death was studied by measuring mitochondrial membrane potential (ΔΨm) using JC-1 probe. The cytotoxicity studies confirms that TSC cobalt complex is having potent anticancer activity on HL-60, K-562, MOLT-4 and COLO-205 cell lines with the IC50 value in the range 0.225-29.00 μM. Dose dependent increase in the LDH release into the surrounding media depicts the cell membrane disintegrity. DNA fragmentation on treated cells revealed the cell death, which is commonly associated with apoptosis. Fluorescence microscopic imaging of treated cells confirms that the mode of cell death was through apoptosis. Loss of the ΔΨm in treated cells explicates the involvement of mitochondria in the cell death induction. Further increase in caspase-3 activity upon treatment corroborates that molecule induces apoptosis. Taken together, this exploratory study revealed that TSC cobalt complex possesses potent cytotoxic and

  5. 99mTc(CO)3 - nitrofuryl thiosemicarbazone a novel infection imaging agent

    Full text: To develop a potential Technetium labeled infection imaging agent 5-NTS prepared and labeled and its scintigraphic imaging done in rat model. Objective: Diagnosis of deep seated infection is a very challenging problem. Differentiation between bacterial infection and sterile inflammation is also difficult. As thiosemicarbazone compound show antibacterial activity, so a new infection imaging agent was prepared. Their in-vitro and in-vitro stability studies, through biological screening and scintigraphic imaging of the chelates labeled with 99mTc studied on infected thigh muscle tissues in rat model. Materials and Methods: Synthesis of 5-nitrofural thiosemicarbazone An equimolar mixture of 5 nitrofural and thiosemicarbazide was stirred with p-TsOH (catalytic amounts) in dry toluene. Synthesized compound characterized by 1H-NMR and ESI-MS. The synthesized compound labeled with 99mTc(CO)3 precursor and 99mTc-oxo(V) core using stannous chloride reduction method. Labeled compound was characterized by TLC in acetone, brine, and ethanol: water: acetic acid: pyridine (1:5:5:1) and also with reverse phase C-18 column. In-vitro stability study was tested in challenge assay with increasing concentration of DTPA (0, 102, 103, 104, 105 molar excess) for 4 hour. Serum stability was also done and its stability analyzed at 0, 2, 8, 18, 24 hour. Infection was induced in rats (Sprague Dawley, 200-220gm) by injecting 0.2 ml of freshly prepared harvested culture of S. aureus (2x108cfu) in left thigh muscle. One day after when the infection was apparent, radiopharmaceutical (185-259 kBq/0.1ml) was injected intravenously. For comparison sterile inflammation was induced by an intramuscular injection of 0.1ml of Terpentine oil I. P. to left thigh muscle. The infected animal with radiopharmaceuticals sacrificed at 1, 4, 8, 24 hour post injection, desired organ were collected and transferred to counting vials. Blood samples were obtained by puncture of the heart. Results: Expressed

  6. Bis(ethanol-κO)bis(pyridine-3-carbaldehyde-κN thiosemicarbazone)bis(thiocyanato-κN)iron(II)–pyridine-3-carbaldehyde thiosemicarbazone (1/2)

    Shao-Mei Wang

    2009-01-01

    The crystal structure of the title FeII complex, [Fe(NCS)2(C7H8N4S)2(CH3CH2OH)2]·2C7H8N4S, based on the Schiff base ligand pyridine-3-carbaldehyde thiosemicarbazone (pct), results from the cocrystallization of an FeII coordination compound together with two of the pct ligands. The complex unit is mononuclear, with the central FeII ion located on a crystallographic centre of inversion and coordinated by four N atoms from two pct ligands and two thiocyanate anions. The slightly distort...

  7. The binding of β-d-glucopyranosyl-thiosemicarbazone derivatives to glycogen phosphorylase: A new class of inhibitors.

    Alexacou, Kyra-Melinda; Tenchiu Deleanu, Alia-Cristina; Chrysina, Evangelia D; Charavgi, Maria-Despoina; Kostas, Ioannis D; Zographos, Spyros E; Oikonomakos, Nikos G; Leonidas, Demetres D

    2010-11-15

    Glycogen phosphorylase (GP) is a promising target for the treatment of type 2 diabetes. In the process of structure based drug design for GP, a group of 15 aromatic aldehyde 4-(β-d-glucopyranosyl)thiosemicarbazones have been synthesized and evaluated as inhibitors of rabbit muscle glycogen phosphorylase b (GPb) by kinetic studies. These compounds are competitive inhibitors of GPb with respect to α-d-glucose-1-phosphate with IC(50) values ranging from 5.7 to 524.3μM. In order to elucidate the structural basis of their inhibition, the crystal structures of these compounds in complex with GPb at 1.95-2.23Å resolution were determined. The complex structures reveal that the inhibitors are accommodated at the catalytic site with the glucopyranosyl moiety at approximately the same position as α-d-glucose and stabilize the T conformation of the 280s loop. The thiosemicarbazone part of the studied glucosyl thiosemicarbazones possess a moiety derived from substituted benzaldehydes with NO(2), F, Cl, Br, OH, OMe, CF(3), or Me at the ortho-, meta- or para-position of the aromatic ring as well as a moiety derived from 4-pyridinecarboxaldehyde. These fit tightly into the β-pocket, a side channel from the catalytic site with no access to the bulk solvent. The differences in their inhibitory potency can be interpreted in terms of variations in the interactions of the aldehyde-derived moiety with protein residues in the β-pocket. In addition, 14 out of the 15 studied inhibitors were found bound at the new allosteric site of the enzyme. PMID:20947361

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

    Mohamed Subarkhan, M.; Ramesh, R.

    2015-03-01

    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 d5) in nature and all the complexes show rhombic distortion around the ruthenium ion with three different 'g' values (gx ≠ gy ≠ gz) at 77 K. All the complexes are redox active and exhibit an irreversible metal centered redox processes (RuIII-RuIII/RuIV-RuIV; RuIII-RuIII/RuII-RuII) within the potential range of 0.38-0.86 V 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 RuVdbnd O species is proposed as catalytic intermediate for the catalytic cycle.

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

    Jörg Schröder

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

  10. Synthesis, structure and biological activity of nickel(II) complexes of 5-methyl 2-furfural thiosemicarbazone.

    Jouad, E M; Larcher, G; Allain, M; Riou, A; Bouet, G M; Khan, M A; Thanh, X D

    2001-09-01

    5-Methyl 2-furfuraldehyde thiosemicarbazone (M5HFTSC) with nickel(II) leads to three types of complexes: [Ni(M5HFTSC)(2)X(2)], [Ni(M5FTSC)(2)] and [Ni(M5FTSC)(2)] x 2DMF. In the first type the ligand remains in thione form, while in the two other, the anionic thiolato form is involved. The species [Ni(M5HFTSC)(2)X(2)] has been characterized spectroscopically. The structures of [Ni(M5FTSC)(2)] x 2DMF and [Ni(M5FTSC)(2)] have been solved using X-ray diffraction. Biological studies of [Ni(M5HFTSC)(2)Cl(2)] have been carried out in vitro for antifungal activity on human pathogenic fungi, Aspergillus fumigatus and Candida albicans, and in vivo for toxicity on mice. The results are compared to those of the ligand, the metal salt and a similar copper complex [Cu(M5HFTSC)Cl(2)]. PMID:11566328

  11. Study on the Interaction between Isatin-β-Thiosemicarbazone and Calf Thymus DNA by Spectroscopic Techniques

    Pakravan, Parvaneh; Masoudian, Shahla

    2015-01-01

    The interaction between isatin-β-thiosemicarbazone (IBT) and calf thymus DNA (CT-DNA) was investigated in physiological buffer (pH 7.4) using Neutral Red (NR) dye as a spectral probe by UV–Vis absorption and fluorescence spectroscopy, as well as viscosity measurements. The IBT is stabilized by intercalation in the DNA (K [IBT –DNA] = 1.03×105 M−1), and displaces the NR dye from the NR–DNA complex. The binding constants Kf and number of binding sites (n≈1) of IBT with DNA were obtained by fluorescence quenching method at different temperatures. Furthermore, the enthalpy and entropy of the reaction between IBT and CT-DNA showed that the reaction is enthalpy-favored and entropy-disfavored. The changes in the base stacking of CT-DNA upon the binding of IBT are reflected in the circular dichroic (CD) spectral studies. The viscosity increase of CT-DNA solution is another evidence to indicate that, IBT is able to be intercalated in the DNA base pairs. PMID:25561917

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

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

    2014-11-01

    A conformationally rigid half-sandwich organoruthenium (II) complex [(η(6)-p-cymene)RuClTSC(N-S)]Cl, (1) and carbonyl complex [Ru(CO)Cl(PPh3)2TSC(N-S)] (2) have been synthesized from the reaction of [{(η(6)-p-cymene)RuCl}2(μ-Cl)2] and [Ru(H)(Cl)(CO)(PPh3)3] with thiophene-2-carboxaldehyde thiosemicarbazon (TSC) respectively and both novel ruthenium (II) complexes have been characterized by elemental analysis, FT-IR and NMR spectroscopy. The peripheral TSC in the complexes acts as an electrochemical coupling unit providing the ability to carry out electrochemical deposition (ED) and to form an electro-deposited film on a graphite electrode surface. The biosensing applicability of complexes 1 and 2 was investigated by using glucose oxidase (GOx) as a model enzyme. Electrochemical measurements at -0.9V versus Ag/AgCl electrode by following the ED Ru(II) reduction/oxidation due to from the enzyme activity, in the presence of glucose substrate. The designed biosensor showed a very good linearity for 0.01-0.5mM glucose. The in vitro antimicrobial activities of complexes 1 and 2 were also investigated against nine bacterial strains and one fungus by the disc diffusion test method. No activity was observed against the Gram-negative strains and fungus, whereas complex 1 showed moderate antibacterial activities against Gram-positive bacterial strains. PMID:25280673

  13. Synthesis and spectral investigations of Mn(II) complexes of pentadentate bis(thiosemicarbazones)

    Krishnan, Suja; Laly, K.; Prathapachandra Kurup, M. R.

    2010-02-01

    Five Mn(II) complexes of bis(thiosemicarbazones) which are represented as [Mn(H 2Ac4Ph)Cl 2] ( 1), [Mn(Ac4Ph)H 2O] ( 2), [Mn(H 2Ac4Cy)Cl 2]·H 2O ( 3), [Mn(H 2Ac4Et)Cl 2]·3H 2O ( 4) and [Mn(H 2Ac4Et)(OAc) 2]·3H 2O ( 5) have been synthesized and characterized by elemental analyses, electronic, infrared and EPR spectral techniques. In all the complexes except [Mn(Ac4Ph)H 2O], the ligands act as pentadentate neutral molecules and coordinate to Mn(II) ion through two thione sulfur atoms, two azomethine nitrogens and the pyridine nitrogen, suggesting a heptacoordination. While in compound [Mn(Ac4Ph)H 2O], the dianionic ligand is coordinated to the metal suggesting six coordination in this case. Magnetic studies indicate the high spin state of Mn(II). Conductivity measurements reveal their non-electrolyte nature. EPR studies indicate five g values for [Mn(Ac4Ph)H 2O] showing zero field splitting.

  14. Intracellular reduction/activation of a disulfide switch in thiosemicarbazone iron chelators

    Akam, Eman A.; Chang, Tsuhen M.; Astashkin, Andrei V.

    2014-01-01

    Iron scavengers (chelators) offer therapeutic opportunities in anticancer drug design by targeting the increased demand for iron in cancer cells as compared to normal cells. Prochelation approaches are expected to avoid systemic iron depletion as chelators are liberated under specific intracellular conditions. In the strategy described herein, a disulfide linkage is employed as a redox-directed switch within the binding unit of an antiproliferative thiosemicarbazone prochelator, which is activated for iron coordination following reduction to the thiolate chelator. In glutathione redox buffer, this reduction event occurs at physiological concentrations and half-cell potentials. Consistent with concurrent reduction and activation, higher intracellular thiol concentrations increase cell susceptibility to prochelator toxicity in cultured cancer cells. The reduction of the disulfide switch and intracellular iron chelation are confirmed in cell-based assays using calcein as a fluorescent probe for paramagnetic ions. The resulting low-spin Fe(III) complex is identified in intact Jurkat cells by EPR spectroscopy measurements, which also document a decreased concentration of active ribonucleotide reductase following exposure to the prochelator. Cell viability and fluorescence-based assays show that the iron complex presents low cytotoxicity and does not participate in intracellular redox chemistry, indicating that this antiproliferative chelation strategy does not rely on the generation of reactive oxygen species. PMID:25100578

  15. EXTRACTIVE SPECTROPHOTOMETRIC STUDIES OF ACETOPHENONE 2’, 4’-DIHYDROXY THIOSEMICARBAZONE WITH IRON

    P. K. Rana

    2012-10-01

    Full Text Available Acetophenone 2’, 4’-Dihydroxy thiosemicarbazone (APDHTS as a reagent for the extractive spectrophotometric determination of Iron. The reagent APDHTS gave instantaneous and stable violet colour with Iron at pH 5.0. A linear calibration graph over the concentration range 1 ppm to 10 ppm with a 3σ limit of detection of 0.66 ppm was obtained by applying the spectrophotometric method at wavelength 370 nm. The stoichiometry of the complex is established as 1:1 (M: L by Job’s method of continuous variation and confirmed by mole ratio method. The standard deviation and the coefficient of variations are presented. The molar absorptivity and Sandal’s sensitivity of the complex is 0.4469 x 103 L mol-1cm –1 and 0.0125 µg cm-2 respectively. The results of the prescribed procedure applied for the determination of the micro amounts of Fe (III in various synthetic and standard steel samples are presented.

  16. Species Dependence of [64Cu]Cu-Bis(thiosemicarbazone) Radiopharmaceutical Binding to Serum Albumins

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

    2008-01-01

    Introduction Interactions of three copper(II) bis(thiosemicarbazone) PET radiopharmaceuticals with human serum albumin, and the serum albumins of four additional mammalian species, were evaluated. Methods 64Cu-labeled diacetyl bis(N4-methylthiosemicarbazonato)copper(II) (Cu-ATSM), pyruvaldehyde bis(N4-methylthiosemicarbazonato)copper(II) (Cu-PTSM), and ethylglyoxal bis(thiosemicarbazonato)copper(II) (Cu-ETS) were synthesized and their binding to human, canine, rat, baboon, and porcine serum albumins quantified by ultrafiltration. Protein binding was also measured for each tracer in human, porcine, rat, and mouse serum. Results The interaction of these neutral, lipophilic copper chelates with serum albumin is highly compound- and species-dependent. Cu-PTSM and Cu-ATSM exhibit particularly high affinity for human serum albumin (HSA), while the albumin binding of Cu-ETS is relatively insensitive to species. At HSA concentrations of 40 mg/mL, “% Free” (non-albumin-bound) levels of radiopharmaceutical were 4.0 ± 0.1%; 5.3 ± 0.2%; and 38.6 ± 0.8% for Cu-PTSM; Cu-ATSM; and Cu-ETS, respectively. Conclusions Species-dependent variations in radiopharmaceutical binding to serum albumin may need to be considered when using animal models to predict the distribution and kinetics of these compounds in humans. PMID:18355683

  17. Simultaneous second derivative spectrophotometric determination of cobalt and vanadium using 2-hydroxy-3-methoxy benzaldehyde thiosemicarbazone

    2-Hydroxy-3-methoxy benzaldehyde thiosemicarbazone reacts with cobalt(II) and vanadium(V) at pH 6.0 forming respectively brown and green coloured complexes in aqueous dimethyl formamide. The second derivative spectrum of Co(II) complex shows zero amplitude at 434.5 nm and considerably large amplitude at 409.5 nm, while V(V) complex shows sufficient amplitude at 434.5 nm and zero amplitude at 409.5 nm. Further, the derivative amplitudes obey Beer's law at 409.5 and 434.5 nm for Co(II) and V(V) in the range 0.059-3.535 and 0.051-4.074 μg/ml, respectively. This enables the simultaneous determination of Co(II) and V(V) without separation. A large number of foreign ions do not interfere in the present method. The method is applied to the simultaneous determination of Co(II) and V(V) in synthetic mixtures and alloy steel samples

  18. Crystal structures of crotonaldehyde semicarbazone and crotonaldehyde thiosemicarbazone from X-ray powder diffraction data.

    Arfan, Atef; Rukiah, Mwaffak

    2015-02-01

    Crotonaldehyde semicarbazone {systematic name: (E)-2-[(E)-but-2-en-1-yl-idene]hydrazinecarboxamide}, C5H9N3O, (I), and crotonaldehyde thio-semi-carba-zone {systematic name: (E)-2-[(E)-but-2-en-1-yldene]hydra-zinecarbo--thio-amide}, C5H9N3S, (II), show the same E conformation around the imine C=N bond. Compounds (I) and (II) were obtained by the condensation of crotonaldehyde with semicarbazide hydro-chloride and thio-semicarbazide, respectively. Each mol-ecule has an intra-molecular N-H⋯N hydrogen bond, which generates an S(5) ring. In (I), the crotonaldehyde fragment is twisted by 2.59 (5)° from the semicarbazide mean plane, while in (II) the corresponding angle (with the thio-semicarbazide mean plane) is 9.12 (5)°. The crystal packing is different in the two compounds: in (I) inter-molecular N-H⋯O hydrogen bonds link the mol-ecules into layers parallel to the bc plane, while weak inter-molecular N-H⋯S hydrogen bonds in (II) link the mol-ecules into chains propagating in [110]. PMID:25878810

  19. Tin(II Selective PVC Membrane Electrode Based on Salicylaldehyde Thiosemicarbazone as an Ionophore

    Sulekh Chandra

    2013-01-01

    Full Text Available A polymeric membrane-based tin selective electrode was developed by using salicylaldehyde thiosemicarbazone (STSC. The best performance was recorded with a membrane composition of PVC : TBP : ionophore : NaTPB as 28 : 59 : 8 : 5 (w/w%. The Nernstian slope calculated from the calibration curve for Sn2+ sensor was 28.8 ± 0.4 mV/decade. The detection limit of the sensor was 2.10 × 10−8 M, in the linear concentration range of 1.0 × 10−2−1.1 × 10−7 M. It was relatively fast response time (<8 s for concentration ≥1.0×10−4 and <12 s for concentration of ≥1.0×10−6 M and can be used for 9 months without any considerable divergence in potentials. The proposed sensor exhibit relatively good selectivity and high sensitivity for tin(II as other mono-, di-, and trivalent cations and can be used in a pH range of 2.0–8.5. The analytical usefulness of the proposed electrode has been evaluated by its application in the determination of stannous in artificially made samples.

  20. Synthesis and biological evaluation of new naphthalene substituted thiosemicarbazone derivatives as potent antifungal and anticancer agents.

    Altıntop, Mehlika Dilek; Atlı, Özlem; Ilgın, Sinem; Demirel, Rasime; Özdemir, Ahmet; Kaplancıklı, Zafer Asım

    2016-01-27

    New thiosemicarbazone derivatives (1-10) were obtained via the reaction of 4-(naphthalen-1-yl)thiosemicarbazide with fluoro-substituted aromatic aldehydes. The synthesized compounds were evaluated for their in vitro antifungal effects against pathogenic yeasts and molds using broth microdilution assay. Ames and umuC assays were carried out to determine the genotoxicity of the most effective antifungal derivatives. Furthermore, all compounds were evaluated for their cytotoxic effects on A549 human lung adenocarcinoma and NIH/3T3 mouse embryonic fibroblast cell lines using XTT test. Among these derivatives, 4-(naphthalen-1-yl)-1-(2,3-difluorobenzylidene)thiosemicarbazide (1) and 4-(naphthalen-1-yl)-1-(2,5-difluorobenzylidene)thiosemicarbazide (3) can be identified as the most promising antifungal derivatives due to their notable inhibitory effects on Candida species and no cytotoxicity against NIH/3T3 mouse embryonic fibroblast cell line. According to Ames and umuC assays, compounds 1 and 3 were classified as non-mutagenic compounds. On the other hand, 4-(naphthalen-1-yl)-1-(2,4-difluorobenzylidene)thiosemicarbazide (2) can be considered as the most promising anticancer agent against A549 cell line owing to its notable inhibitory effect on A549 cells with an IC50 value of 31.25 μg/mL when compared with cisplatin (IC50 = 16.28 μg/mL) and no cytotoxicity against NIH/3T3 cells. PMID:26706351

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

    Introduction: Interactions of three copper(II) bis(thiosemicarbazone) positron emission tomography radiopharmaceuticals with human serum albumin, and the serum albumins of four additional mammalian species, were evaluated. Methods: 64Cu-labeled diacetyl bis(N4-methylthiosemicarbazonato)copper(II) (Cu-ATSM), pyruvaldehyde bis(N4-methylthiosemicarbazonato)copper(II) (Cu-PTSM) and ethylglyoxal bis(thiosemicarbazonato)copper(II) (Cu-ETS) were synthesized and their binding to human, canine, rat, baboon and porcine serum albumins quantified by ultrafiltration. Protein binding was also measured for each tracer in human, porcine, rat and mouse serum. Results: The interaction of these neutral, lipophilic copper chelates with serum albumin is highly compound- and species-dependent. Cu-PTSM and Cu-ATSM exhibit particularly high affinity for human serum albumin (HSA), while the albumin binding of Cu-ETS is relatively insensitive to species. At HSA concentrations of 40 mg/ml, '% free' (non-albumin-bound) levels of radiopharmaceutical were 4.0±0.1%, 5.3±0.2% and 38.6±0.8% for Cu-PTSM, Cu-ATSM and Cu-ETS, respectively. Conclusions: Species-dependent variations in radiopharmaceutical binding to serum albumin may need to be considered when using animal models to predict the distribution and kinetics of these compounds in humans

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

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

    2008-04-15

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

  3. Structural, thermal and optical characterization of an organic NLO material—Benzaldehyde thiosemicarbazone monohydrate single crystals

    Santhakumari, R.; Ramamurthi, K.

    2011-02-01

    Single crystals of the organic NLO material, benzaldehyde thiosemicarbazone (BTSC) monohydrate, were grown by slow evaporation method. Solubility of BTSC monohydrate was determined in ethanol at different temperatures. The grown crystals were characterized by single crystal X-ray diffraction analysis to determine the cell parameters and by FT-IR technique to study the presence of the functional groups. Thermogravimetric and differential thermal analyses reveal the thermal stability of the crystal. UV-vis-NIR spectrum shows excellent transmission in the region of 200-1100 nm. Theoretical calculations were carried out to determine the linear optical constants such as extinction coefficient and refractive index. Further the optical nonlinearities of BTSC have been investigated by Z-scan technique with He-Ne laser radiation of wavelength 632.8 nm. Mechanical properties of the grown crystal were studied using Vickers microhardness tester. Second harmonic generation efficiency of the powdered BTSC monohydrate was tested using Nd:YAG laser and it is found to be ˜5.3 times that of potassium dihydrogen orthophosphate.

  4. Study on the Interaction between Isatin-β-Thiosemicarbazone and Calf Thymus DNA by Spectroscopic Techniques.

    Pakravan, Parvaneh; Masoudian, Shahla

    2015-01-01

    The interaction between isatin-β-thiosemicarbazone (IBT) and calf thymus DNA (CT-DNA) was investigated in physiological buffer (pH 7.4) using Neutral Red (NR) dye as a spectral probe by UV-Vis absorption and fluorescence spectroscopy, as well as viscosity measurements. The IBT is stabilized by intercalation in the DNA (K [IBT -DNA] = 1.03×10(5) M(-1)), and displaces the NR dye from the NR-DNA complex. The binding constants Kf and number of binding sites (n≈1) of IBT with DNA were obtained by fluorescence quenching method at different temperatures. Furthermore, the enthalpy and entropy of the reaction between IBT and CT-DNA showed that the reaction is enthalpy-favored and entropy-disfavored. The changes in the base stacking of CT-DNA upon the binding of IBT are reflected in the circular dichroic (CD) spectral studies. The viscosity increase of CT-DNA solution is another evidence to indicate that, IBT is able to be intercalated in the DNA base pairs. PMID:25561917

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

    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

  6. Spectrophotometric Determination of Arsenic in Water Samples by Thiophene-2-Carboxaldehyde Thiosemicarbazone impregnated with alumina

    Md. Faridur Rahman

    2015-12-01

    Full Text Available Thiophene-2-carboxaldehyde thiosemicarbazone has been successfully applied as an analytical reagent for micro level solid phase spectrophotometric determination of As (III at pH 3.5. Here it can be seen that arsenic reacts with the new chelating ligand in acidic medium to form the As (III-tctsc complex. The complex showed maximum absorbance at λ max 281 nm for As (III ions. The Beer’s law range was 0.1-1.0 mg/L. Job’s method and Mole-ratio method showed that As (III-ligand ratio in the complex is 1:2. The Molar absorptivity and Sandell’s sensitivity were 5.96 x 104 L mol-1 cm-1 and 0.01μg/cm2 respectively for As (III ions. The proposed method has been successfully applied to the determination of arsenic in drinking water samples of Kaliachak, in the district of Malda, West Bengal, India.

  7. 2-Butyl-4-chloroimidazole based substituted piperazine-thiosemicarbazone hybrids as potent inhibitors of Mycobacterium tuberculosis.

    Jallapally, Anvesh; Addla, Dinesh; Yogeeswari, Perumal; Sriram, Dharmarajan; Kantevari, Srinivas

    2014-12-01

    Here a series of 2-butyl-4-chloroimidazole based substituted piperazine-thiosemicarbazone hybrids were designed by combining three different pharmacophoric fragments in single molecular architecture. 2-Butyl-4-chloro-1-(3-(4-substituted)piperazin-1-yl)propyl)-1H-imidazole-5-carbaldehydes (4a-p) prepared by reacting carboxaldehyde 2 with N-alkyl piperazines 3a-p which were condensed with thiosemicarbazine to give desired compounds 5a-p in very good yields. Among all sixteen compounds screened for in vitro antimycobacterial activity against Mycobacterium tuberculosis H37Rv (MTB), two compounds (E)-2-((2-butyl-4-chloro-1-(3-(4-(o-tolyl) piperazin-1-yl)propyl)-1H-imidazol-5-yl)methylene)hydrazinecarbothioamide 5e and (E)-2-((2-butyl-4-chloro-1-(3-(4-(2-methoxyphenyl)piperazin-1-yl)propyl)-1H-imidazol-5-yl)methylene) hydrazine carbothioamide 5f were found to be the most potent antitubercular agents (MIC: 3.13 μg/mL) with low toxicity profile. PMID:25451998

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

    Zafer Asım Kaplancıklı

    2016-01-01

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

  9. Intracellular reduction/activation of a disulfide switch in thiosemicarbazone iron chelators.

    Akam, Eman A; Chang, Tsuhen M; Astashkin, Andrei V; Tomat, Elisa

    2014-10-01

    Iron scavengers (chelators) offer therapeutic opportunities in anticancer drug design by targeting the increased demand for iron in cancer cells as compared to normal cells. Prochelation approaches are expected to avoid systemic iron depletion as chelators are liberated under specific intracellular conditions. In the strategy described herein, a disulfide linkage is employed as a redox-directed switch within the binding unit of an antiproliferative thiosemicarbazone prochelator, which is activated for iron coordination following reduction to the thiolate chelator. In glutathione redox buffer, this reduction event occurs at physiological concentrations and half-cell potentials. Consistent with concurrent reduction and activation, higher intracellular thiol concentrations increase cell susceptibility to prochelator toxicity in cultured cancer cells. The reduction of the disulfide switch and intracellular iron chelation are confirmed in cell-based assays using calcein as a fluorescent probe for paramagnetic ions. The resulting low-spin Fe(III) complex is identified in intact Jurkat cells by EPR spectroscopy measurements, which also document a decreased concentration of active ribonucleotide reductase following exposure to the prochelator. Cell viability and fluorescence-based assays show that the iron complex presents low cytotoxicity and does not participate in intracellular redox chemistry, indicating that this antiproliferative chelation strategy does not rely on the generation of reactive oxygen species. PMID:25100578

  10. Synthesis and characterization of some novel antimicrobial thiosemicarbazone O-carboxymethyl chitosan derivatives.

    Mohamed, Nadia A; Mohamed, Riham R; Seoudi, Rania S

    2014-02-01

    Three novel thiosemicarbazone O-carboxymethyl chitosan derivatives were obtained via a condensation reaction of thiosemicarbazide O-carboxymethyl chitosan with o-hydroxybenzaldehyde, p-methoxybenzaldehyde, and p- chlorobenzaldehyde respectively. Their structures were characterized by elemental analysis, FTIR, (13)C NMR and X-ray diffraction. The antimicrobial behaviors of the prepared derivatives against three types of bacteria Staphylococcus aureus (S. aureus, RCMBA 2004), Bacillus subtilis (B. subtilis, RCMBA 6005), and Escherichia coli (E. Coli, RCMBA 5003) and three crops-threatening pathogenic fungi Aspergillus fumigatus (A. fumigatus, RCMBA 06002), Geotrichum candidum (G. candidum, RCMB 05098), and Candida albicans (C. albicans, RCMB 05035) were investigated. The results indicated that the antibacterial and antifungal activities of the investigated derivatives are much higher than those of the parent O-carboxymethyl chitosan. They were more potent in case of Gram-positive bacteria than Gram-negative bacteria. The presence of electron withdrawing chlorine atom on the aryl moiety of the aldehyde portion improved greatly antimicrobial activity to be nearly equivalent to the used standard drugs. PMID:24211430

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

    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.

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

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

    2013-12-01

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

  13. Synthesis and Toxicity Evaluation of Some N4-Aryl Substituted 5-Trifluoromethoxyisatin-3-thiosemicarbazones

    Muhammad Yaqub

    2011-07-01

    Full Text Available A series of twenty one N4-aryl substituted 5-trifluoromethoxyisatin-3-thiosemicarbazones 3a-3u was synthesized by the reaction of trifluoromethoxyisatin 1 with different arylthiosemicarbazides 2 in aqueous ethanol (50%, containing a few drops of acetic acid. Their structures were established on the basis of analytical (CHN and spectral (IR, 1H-NMR, EIMS data. All the synthesized compounds were evaluated for their toxicity potential by a brine shrimp lethality bioassay. Ten compounds i.e., 3a, 3e, 3i-3l and 3n-3q proved to be active in this assay, displaying promising toxicity (LD50 = 1.11 × 10−5 M − 1.80 × 10−4 M. Amongst these, 3k, 3n and 3o were found to be the most active ones (LD50 = 1.11 × 10−5 M − 1.43 × 10−5 M. Compound 3k showed the highest activity with a LD50 value of 1.11 × 10−5 M and can, therefore, be used as a lead for further studies. Structure-activity relationship (SAR studies revealed that the presence of strong inductively electron-attracting trifluoromethoxy substituent at position-5 of the isatin moiety played an important role in inducing or enhancing toxic potentiality of some of the synthesized compounds.

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

    Elizandra Aparecida Britta

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

  15. Antiviral activity of platinum (II) and palladium (II) complexes of pyridine-2-carbaldehyde thiosemicarbazone.

    Varadinova, T; Kovala-Demertzi, D; Rupelieva, M; Demertzis, M; Genova, P

    2001-04-01

    A heterocyclic compound, pyridine-2-carbaldehyde thiosemicarbazone (HFoTsc), and its six metal coordinated bound complexes, three with platinum (II) and three with palladium (II), were studied for their activity against herpes simplex virus 1 (HSV-1) infection in cultured cells. According to their cytotoxicity the compounds were divided into two groups. Group I (cytotoxic compounds) included all three palladium complexes and [Pt(HFoTsc)2] Cl2, with maximum non-toxic concentration (MNC) of 1-10 micromol/l and a 50% cytotoxic concentration (CC50) of 20-100 micromol/l. Group 2 (low cytotoxic compounds) with MNC of 100 micromol/l and CC50 of 548-5820 micromol/l included compounds in the following order: [Pt(HFoTsc)2] Cl2antiviral activity. IC50 and SI values of HFoTsc increased in parallel with the duration of action in HSV-1-infected cells. All three platinum complexes as well as [Pd(HFoTsc)2]Cl2 and [Pd(FoTsc)2] inhibited HSV- I infection following a structure-activity relationship but only [Pt(HFoTsc)2]Cl2 expressed a significant selectivity comparable to that of HFoTsc. However, [PdCl(FoTsc)] acting 48 hrs gave a higher infectious HSV-1 titer (170%) compared to control (100%, no compound). PMID:11719987

  16. Crystal structures of crotonaldehyde semicarbazone and crotonaldehyde thiosemicarbazone from X-ray powder diffraction data

    Atef Arfan

    2015-02-01

    Full Text Available Crotonaldehyde semicarbazone {systematic name: (E-2-[(E-but-2-en-1-ylidene]hydrazinecarboxamide}, C5H9N3O, (I, and crotonaldehyde thiosemicarbazone {systematic name: (E-2-[(E-but-2-en-1-yldene]hydrazinecarbothioamide}, C5H9N3S, (II, show the same E conformation around the imine C=N bond. Compounds (I and (II were obtained by the condensation of crotonaldehyde with semicarbazide hydrochloride and thiosemicarbazide, respectively. Each molecule has an intramolecular N—H...N hydrogen bond, which generates an S(5 ring. In (I, the crotonaldehyde fragment is twisted by 2.59 (5° from the semicarbazide mean plane, while in (II the corresponding angle (with the thiosemicarbazide mean plane is 9.12 (5°. The crystal packing is different in the two compounds: in (I intermolecular N—H...O hydrogen bonds link the molecules into layers parallel to the bc plane, while weak intermolecular N—H...S hydrogen bonds in (II link the molecules into chains propagating in [110].

  17. Technetium(I) tricarbonyl complexed with the N-heterocyclic aldehyde thiosemicarbazones: potential precursors of the radiopharmaceuticals

    Technetium(I) tricarbonyl complexes may form with the pyridine aldehyde thiosemicarbazones (TSCs), in which chelating ligand is bound tri- or bidentately. Intend of the presented work was to check, if labeling the N-heterocyclic TSCs with tricarbonyl [99mTc]-technetium(I) may lead to formation of the complexes suitable for the radiopharmaceutical purposes. Syntheses of the complexes were provided in the conditions analogous to those performed in the nuclear medicine laboratories. Main physicochemical properties of the complexes important in the medicinal chemistry were studied. Relevant results of the numerical calculations remain in fair agreement with these properties. (author)

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

    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.

  19. Cytotoxic and Antitumour Studies of Acetoacetanilide N(4)-methyl(phenyl)thiosemicarbazone and its Transition Metal Complexes

    Priya, N. P.; Firdous, A. P.; Jeevana, R.; Aravindakshan, K. K.

    2015-01-01

    Cytotoxic activities of acetoacetanilide N(4)-methyl(phenyl)thiosemicarbazone (L2H) and its seven different metal complexes were studied. Of these, IC50 value of the copper complex was found to be 46 μg/ml. Antitumour studies of this copper complex was carried out using Daltons Lymphoma Ascites cell-induced solid tumour model and Ehrlich's Ascites Carcinoma cell-induced ascites tumour model. Administration of the copper complex at different concentrations (10, 5 and 1 mg/kg b. wt) inhibited t...

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

    Solid complexes of α-oximinoacetoacetanilide thiosemicarbazone (OAATS) with Ni(II), Co(II), Zn(II), Mn(II), Cd(II), Hg(II) and UO2(II) have been prepared and characterized on the basis of their elemental analyses, conductivity, differential scanning calorimetry, thermogravimetric analysis, infrared and electronic spectral measurements, in conjunction with magnetic susceptibility measurements. Molecular orbital calculations employing the CNDO/2 method have been made for a number of conformations of the ligand molecule to ascertain the most stable one. (author). 24 refs., 3 figs., 2 tabs

  1. Effect of Diacetyl Monoxime Thiosemicarbazone on the Corrosion of Aged 18 Ni 250 Grade Maraging Steel in Sulphuric Acid Solution

    T. Poornima

    2012-01-01

    Full Text Available The corrosion inhibition of the aged 18 Ni 250 grade maraging steel in 0.5 M sulphuric acid by diacetyl monoxime thiosemicarbazone (DAMTSC at 303–323 K has been investigated by potentiodynamic polarization, EIS, and SEM techniques. Good inhibition efficiency of DAMTSC was revealed even at low concentrations, which increased with the increase in DAMTSC concentration and decreased with the increase in temperature. The activation energies, , as well as other thermodynamic parameters (; ; , were evaluated and discussed. The adsorption of DAMTSC on the aged maraging steel surface was found to obey the Langmuir adsorption isotherm model and shows mixed type inhibition behavior.

  2. Synthesis, spectral and thermal studies of some lanthanide(III) complexes of 4-[N-(benzalidene) amino] antipyrine thiosemicarbazone

    A new series of sixteen lanthanide(III) complexes of 4[N-(benzalidene) amino] antipyrine thiosemicarbazone (BAAPTS) with the general composition LnX3.n(BAAPTS) (X =Cl-, n = 2; X = NO-3, n = 1; Ln = La, Pr, Nd, Sm, Gd, Tb, Dy and Ho) have been synthesized and characterized by chemical analysis, conductance, molar weight, magnetic moments measurements, infrared and electronic spectra. The ligand BAAPTS behaves as neutral tridentate (N, N, S) ligand. The probable coordination number is nine in these complexes. (author)

  3. [Spectroscopic studies on the formation of metal complexes and on the protein binding of antiviral thiosemicarbazone derivatives (author's transl)].

    Heinisch, L; Kramarczyk, K; Tonew, M; Hesse, G

    1981-04-01

    The complexation of some thiosemicarbazones and isothiosemicarbazones of isatin and quinolin-2-aldehydes with Cu2+, Zn2+ and Mn2+ ions was spectrometrically investigated. Semiquantitative data, obtained from extinction values, about the relative complexing tendencies within some groups of homologous substances were brought in relation to their antiviral effects and binding to bovine serum albumin. The complexing tendencies were greatest in compounds with methyl substituents and decreased for higher alkyl substituents. whereas the binding to protein increased in the same order. The well-known maxima of the antiviral observed with medium alkyl groups may be explained by a superposition of these effects. PMID:7255526

  4. Synthesis, nuclear magnetic resonance and infrared studies of zinc(II) and cadmium(II) complexes of thiosemicarbazones derived from fluorenone and p-anisaldehyde

    Fluorenone (FTSCH) and p-anisaldehyde (ATSCH) thiosemicarbazones react with zinc(II) and cadmium(II) acetates forming M:L 1:2 complexes, characterized by IR, 1H and 13C NMR spectra and elemental analyses. The coordination mode of the ligands is discussed and four-coordinate, pseudo-tetrahedral structures are suggested. (author)

  5. Spectral and structural studies of copper(II) complexes of thiosemicarbazones derived from salicylaldehyde and containing ring incorporated at N(4)-position

    Latheef, Leji; Kurup, Maliyeckal R. Prathapachandra

    2008-06-01

    Mononuclear and binuclear copper(II) complexes ( 1- 8) with two ONS donor thiosemicarbazone ligands {salicylaldehyde 3-hexamethyleneiminyl thiosemicarbazone [H 2L 1] and salicylaldehyde 3-tetramethyleneiminyl thiosemicarbazone [H 2L 2]} have been prepared and physico-chemically characterized. IR, electronic and EPR spectra of the complexes have been obtained. The thiosemicarbazones bind to metal as dianionic ONS donor ligands in all the complexes except in [Cu(HL 1) 2] ( 2) and [Cu(HL 2) 2] ( 6). In compounds 2 and 6 the ligands are coordinated as monoanionic HL - ones. The magnetic susceptibility measurements indicate that all the complexes are paramagnetic. In complex [(CuL 1) 2] ( 1), the magnetic moment value is lower than the expected spin only value. In all the complexes g|| > g⊥ > 2.0023 and G values within the range 2.5-3.5 are consistent with d ground state. The complexes were given the formula as [(CuL 1) 2] ( 1); [Cu(HL 1) 2] ( 2); [CuL 1bpy] ( 3); [CuL 1phen] ( 4); [CuL 1γ-pic]·2H 2O ( 5); [Cu(HL 2) 2] ( 6); [CuL 2py]·3H 2O ( 7); [CuL 2bipy] ( 8). The structure of the compound 8 have been solved by single crystal X-ray crystallography and was found to be distorted square pyramid around copper(II) ion.

  6. Inhibitory effect of synthetic aromatic heterocycle thiosemicarbazone derivatives on mushroom tyrosinase: Insights from fluorescence, (1)H NMR titration and molecular docking studies.

    Xie, Juan; Dong, Huanhuan; Yu, Yanying; Cao, Shuwen

    2016-01-01

    Three structurally similar aromatic heterocyclic compounds 2-thiophenecarboxaldehyde (a), 2-furaldehyde (b), 2-pyrrolecarboxaldehyde (c) were chosen and a series of their thiosemicarbazone derivatives(1a-3a, 1b-3b and 1c-3c) were synthesized to evaluate their biological activities as mushroom tyrosinase inhibitors. The inhibitory effects of these compounds on tyrosinase were investigated by using spectrofluorimetry, (1)H NMR titration and molecular docking techniques. From the results of fluorescence spectrum and (1)H NMR titration, it was found that forming complexes between the sulfur atom from thiourea and copper ion of enzyme center may play a key role for inhibition activity. Moreover, investigation of (1)H NMR spectra further revealed that formation of hydrogen bond between inhibitor and enzyme may be helpful to above complexes formation. The results were well coincident with the suggestion of molecular docking and obviously showed that 2-thiophone N(4)-thiosemicarbazone (1a), 2-furfuran N(4)-thiosemicarbazone (1b) and 2-pyrrole N(4)-thiosemicarbazone (1c) are potential inhibitors which deserves further investigation. PMID:26213029

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

    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

    2015-02-01

    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. PMID:25559246

  8. Synthesis and characterization of complexes of monoacetylferrocene-4-phenyl thiosemicarbazone with UO22+, Hg2+, Ni2+ or Zn2+ ions

    Complexes have been synthesized with monoacetylferrocene-4-phenyl thiosemicarbazone (L) combining with UO22+, Hg2+, Ni2+ or Zn2+ ions and characterized through elemental analysis, IR spectrum, UV spectrum and 1HNMR spectrum. The thermal stability and molar conductance have been studied. It shows that L coordinates to the metal ion in a Keto form and is a bidentate ligand

  9. Potentiometric studies on complexation equilibria between some transition metal ions and 2-hydroxy-1-naphthaldehyde thiosemicarbazone in dioxane-water medium

    In continuation of our study on the metal complexes of biologically active o-hydroxynaphthaldehyde and its derivatives, potentiometric studies on the chelation behaviour of bivalent metal complexes of 2-hydroxy-1-naphthaldehyde thiosemicarbazone are described. (author). 11 refs., 2 tabs

  10. Synthetic, structural and kinetic studies on the binding of cyclohexane-1,2-bis(4-methyl-3-thiosemicarbazone) to divalent metal ions (Co, Ni, Cu, Zn or Cd).

    Al-Karawi, Ahmed Jasim M; Clegg, William; Harrington, Ross W; Henderson, Richard A

    2009-01-21

    The reactions of cyclohexane-1,2-bis(4-methyl-3-thiosemicarbazone) (CHMTSC) with MCl2 (M = Co, Ni, Cu or Zn) and Cd(NO3)2 have been shown to produce complexes in which the thiosemicarbazone has been doubly deprotonated [[M(CHMTSC - 2H+)] (M = Co, Ni or Ni)], analogous to those reported earlier with other Schiff base thiosemicarbazones. However, with ZnCl2 and Cd(NO3)2, the complexes isolated are [ZnCl(CHMTSC)]Cl and [Cd(NO3)(CHMTSC)]NO3, containing the protonated forms of the ligand, which have been characterised by X-ray crystallography, as has free CHMTSC. The kinetics of the reactions between CHMTSC and all the various metal salts have been determined by stopped-flow spectrophotometry. In all cases, the reactions are complete on the seconds timescale. The reactions exhibit a first-order dependence on the concentration of metal salt and a first-order dependence on the concentration of CHMTSC. The thermodynamic and kinetic factors influencing the protonation state of the coordinated thiosemicarbazone are discussed. PMID:19122915

  11. Effects of terminal dimethylation and metal coordination of proline-2-formylpyridine thiosemicarbazone hybrids on lipophilicity, antiproliferative activity, and hR2 RNR inhibition.

    Bacher, Felix; Dömötör, Orsolya; Kaltenbrunner, Maria; Mojović, Miloš; Popović-Bijelić, Ana; Gräslund, Astrid; Ozarowski, Andrew; Filipovic, Lana; Radulović, Sinisa; Enyedy, Éva A; Arion, Vladimir B

    2014-12-01

    The nickel(II), copper(II), and zinc(II) complexes of the proline-thiosemicarbazone hybrids 3-methyl-(S)-pyrrolidine-2-carboxylate-2-formylpyridine thiosemicarbazone (L-Pro-FTSC or (S)-H2L(1)) and 3-methyl-(R)-pyrrolidine-2-carboxylate-2-formylpyridine thiosemicarbazone (D-Pro-FTSC or (R)-H2L(1)), as well as 3-methyl-(S)-pyrrolidine-2-carboxylate-2-formylpyridine 4,4-dimethyl-thiosemicarbazone (dm-L-Pro-FTSC or (S)-H2L(2)), namely, [Ni(L-Pro-FTSC-2H)]2 (1), [Ni(D-Pro-FTSC-2H)]2 (2), [Ni(dm-L-Pro-FTSC-2H)]2 (3), [Cu(dm-L-Pro-FTSC-2H)] (6), [Zn(L-Pro-FTSC-2H)] (7), and [Zn(D-Pro-FTSC-2H)] (8), in addition to two previously reported, [Cu(L-Pro-FTSC-2H)] (4), [Cu(D-Pro-FTSC-2H)] (5), were synthesized and characterized by elemental analysis, one- and two-dimensional (1)H and (13)C NMR spectroscopy, circular dichroism, UV-vis, and electrospray ionization mass spectrometry. Compounds 1-3, 6, and 7 were also studied by single-crystal X-ray diffraction. Magnetic properties and solid-state high-field electron paramagnetic resonance spectra of 2 over the range of 50-420 GHz were investigated. The complex formation processes of L-Pro-FTSC with nickel(II) and zinc(II) were studied in aqueous solution due to the excellent water solubility of the complexes via pH potentiometry, UV-vis, and (1)H NMR spectroscopy. The results of the antiproliferative activity in vitro showed that dimethylation improves the cytotoxicity and hR2 RNR inhibition. Therefore, introduction of more lipophilic groups into thiosemicarbazone-proline backbone becomes an option for the synthesis of more efficient cytotoxic agents of this family of compounds. PMID:25391085

  12. Synthesis and spectral feature of benzophenone-substituted thiosemicarbazones and their Ni(II) and Cu(II) complexes

    El-Asmy, A. A.; Al-Hazmi, G. A. A.

    2009-01-01

    The ligational behavior of 2-hydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone N-substituted thiosemicarbazones towards Ni(II) and Cu(II) ions has been investigated. The isolated complexes were identified by elemental analyses, molar conductance, magnetic moment, IR, UV-vis and ESR spectral studies. The IR spectra indicated that the investigated thiosemicarbazones lost the N 2 proton or the N 2 and OH protons and act as mononegative or binegative tridentate ligands. The ligands containing methoxy group facilitate the deprotonation of OH by resonance more than the SH. Most of the Ni(II) complexes measured subnormal magnetic moments due to square-planar + tetrahedral configuration and supported by the electronic spectra. The percentage of square-planar to tetrahedral was calculated and found in agreement with the ligand splitting energy (10Dq). Also, Cu(II) complexes measured subnormal values due to the interaction between copper centers; the lower the value the higher the interaction. It was found that the substitutent has a noticeable effect on the distortion of the complex. The ESR spectra of some solid Cu(II) complexes at room temperature exhibit g|| > g⊥ > 2.0023 confirming a square-planar structure.

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

    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. PMID:25659415

  14. Cyclometallated ruthenium(II) carbonyl complexes with 1-pyrenaldehyde 4-R-3-thiosemicarbazones: Regioselective ruthenation of the 1-pyrenyl group

    Rupesh Narayana Prabhu; Samudranil Pal

    2015-04-01

    A facile method for the synthesis of a series of cyclometallated ruthenium(II) carbonyl complexes with 1-pyrenaldehyde 4-R-3-thiosemicarbazones (H2Ln where the two H’s represent the dissociable thioamide and pyrenyl protons; R = H, Me and Ph) has been described. The characterization of the complexes having the general molecular formula trans-[Ru(Ln)(CO)(EPh33)2] (where E = P or As) were accomplished by elemental (CHN) analysis, magnetic susceptibility and spectroscopic (ESI-MS, IR, UV-Vis, emission and 1H-NMR) measurements. Electronic spectra of the complexes display multiple strong absorptions in the range 440–224 nm due to intraligand transitions. All the complexes exhibit emission bands that are characteristic of ligand centred emissive states. X-ray diffraction studies with representative complexes reveal a pincer-like 5,5-membered fused chelate rings forming CNS coordination mode of the thiosemicarbazonate ligand (Ln)2− via regioselective activation of 1-pyrenyl ortho C–H and formation of a distorted octahedral C2NSE2 coordination sphere around the ruthenium(II) centre.

  15. Copper(II) bis(thiosemicarbazone) complexes as potential tracers for evaluation of cerebral and myocardial blood flow with PET

    Wider application of positron emission tomography would be facilitated by the availability of positron-emitting radiopharmaceuticals labeled with nuclides, like 62Cu, that are available from parent/daughter generator systems. Using a longer-lived copper isotope (67Cu) we have examined three derivatives of copper(II) pyruvaldehyde bis(thiosemicarbazone) as potential tracers for evaluation of cerebral and myocardial blood flow: Cu(PTS), Cu(PTSM), and Cu(PTSM2) (where PTS = pyruvaldehyde bis(thiosemicarbazone), PTSM = pyruvaldehyde bis(N4-methylthiosemicarbazone), and PTSM2 = pyruvaldehyde bis(N4-dimethylthiosemicarbazone). All three lipophilic radiocopper complexes were obtained in high yield via a procedure that could be adapted to a ''kit'' formulation. In animal model systems Cu(PTSM) and Cu(PTSM2) show excellent uptake in the brain and heart following i.v. injection. These tracers differ in that Cu(PTSM) exhibits microsphere-like retention in the brain and heart, whereas Cu(PTSM2) substantially clears from these organs. The relative cerebral pharmacokinetics of [67Cu]Cu(PTSM) and [67Cu]Cu(PTSM2) are consistent with their known reactivity towards intracellular sulfhydryl groups

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

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

    2016-04-01

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

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

    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.

  18. Toxic effects of bis(thiosemicarbazone) compounds and its palladium(II) complexes on herpes simplex virus growth

    Here, we present data on the activity of benzyl bis(thiosemicarbazone); 3,5-diacyl-1,2,4-triazole bis(4-methylthiosemicarbazone) and their Pd(II) complexes against the replication of wild type and of acyclovir (ACV)-resistant, herpes simplex virus type 1 (HSV 1) and type 2 (HSV 2) strains. The data were compared to those under the action of acyclovir. The testing of cytotoxic activity suggests that these compounds may be endowed with important antiviral properties. It is interesting to note that the Pd(II)-benzyl bis(thiosemicarbazone) complex, 2, exhibits a significant activity against acyclovir-resistant viruses R-100 (HSV 1) and PU (HSV 2) with an in vitro selectivity index (SI) of 8.0 vs. 0.01 for acyclovir. This complex also negatively influenced the expression of key structural HSV 1 proteins (VP23, gH and gG/gD), thus suppressing simultaneously virus entry, transactivation of virus genome, capsid assembly, and cell-to-cell spread of infectious HSV progeny

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

    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

    2015-11-01

    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. PMID:26454648

  20. Synthesis, spectroscopic characterization, structural studies and antibacterial and antitumor activities of diorganotin complexes with 3-methoxysalicylaldehyde thiosemicarbazone

    Khandani, Marzieh; Sedaghat, Tahereh; Erfani, Nasrollah; Haghshenas, Mohammad Reza; Khavasi, Hamid Reza

    2013-04-01

    Three organotin(IV) complexes, Ph2Sn(mstsc) (1), Me2Sn(mstsc) (2) and Bu2Sn(mstsc) (3), have been synthesized from reaction of R2SnCl2 (R = Ph, Me and Bu) with 3-methoxysalicylaldehyde thiosemicarbazone (H2mstsc). The synthesized complexes have been characterized by elemental analysis and FT-IR, 1H, 13C and 119Sn NMR spectroscopy. The structures of 2 and 3 have been also confirmed by X-ray crystallography. On the basis of spectral and structural data thiosemicarbazone acts as a tridentate dianionic ligand and coordinates to tin through phenolic oxygen, the azomethine nitrogen and thiolate sulfur atoms. The metal coordination geometry for 2 and 3 is described as distorted square pyramid and the crystal lattices are stabilized by intermolecular hydrogen bands. On the basis of 119Sn NMR data, coordination number of tin retains five in solution. The in vitro antibacterial activity of ligand and its complexes has been evaluated against one Gram-positive and three Gram-negative bacteria. Complex 2 exhibited good activity along with the standard antibacterial drugs. The in vitro cytotoxicities of the synthesized compounds against Jurkat cells were evaluated by the standard WST-1 assay. The activity decreases in the order 3 > 1 > 2 = H2mstsc.

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

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

    2016-01-01

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

  2. Experimental and theoretical evaluation of two pyridinecarboxaldehyde thiosemicarbazone compounds as corrosion inhibitors for mild steel in hydrochloric acid solution

    Highlights: •The studied inhibitors contain both pyridine ring and Schiff’s base structure. •The inhibitors show good inhibitive properties for mild steel in HCl. •The inhibitors adsorb on mild steel surface both physically and chemically. •The PZC measurements show the mild steel surface was positively charged. -- Abstract: The inhibition effect of two Schiff’s base derivatives on the corrosion of mild steel in 1.0 M HCl solution was studied by electrochemical techniques, SEM and theoretical calculation methods. The experimental results show that the inhibition efficiency of 2-pyridinecarboxaldehyde thiosemicarbazone (2-PCT) is higher than that of 4-pyridinecarboxaldehyde thiosemicarbazone (4-PCT), and both the two compounds are good inhibitors for mild steel in 1.0 M HCl. Potentiodynamic polarization curves show that the two inhibitors act as mixed type inhibitors. The adsorption of inhibitors obeys the Langmuir adsorption isotherm, and the thermodynamic parameters (Ea, Kads, ΔGads0) were calculated and discussed. The mechanism of inhibition was determined by PZC measurements and theoretical calculation methods

  3. Copper(II) bis(thiosemicarbazone) complexes as potential tracers for evaluation of cerebral and myocardial blood flow with PET

    Green, M.A.; Klippenstein, D.L.; Tennison, J.R.

    1988-09-01

    Wider application of positron emission tomography would be facilitated by the availability of positron-emitting radiopharmaceuticals labeled with nuclides, like /sup 62/Cu, that are available from parent/daughter generator systems. Using a longer-lived copper isotope (/sup 67/Cu) we have examined three derivatives of copper(II) pyruvaldehyde bis(thiosemicarbazone) as potential tracers for evaluation of cerebral and myocardial blood flow: Cu(PTS), Cu(PTSM), and Cu(PTSM2) (where PTS = pyruvaldehyde bis(thiosemicarbazone), PTSM = pyruvaldehyde bis(N4-methylthiosemicarbazone), and PTSM2 = pyruvaldehyde bis(N4-dimethylthiosemicarbazone). All three lipophilic radiocopper complexes were obtained in high yield via a procedure that could be adapted to a ''kit'' formulation. In animal model systems Cu(PTSM) and Cu(PTSM2) show excellent uptake in the brain and heart following i.v. injection. These tracers differ in that Cu(PTSM) exhibits microsphere-like retention in the brain and heart, whereas Cu(PTSM2) substantially clears from these organs. The relative cerebral pharmacokinetics of (/sup 67/Cu)Cu(PTSM) and (/sup 67/Cu)Cu(PTSM2) are consistent with their known reactivity towards intracellular sulfhydryl groups.

  4. Novel 3,4-methylenedioxyde-6-X-benzaldehyde-thiosemicarbazones: Synthesis and antileishmanial effects against Leishmania amazonensis.

    de Melos, Jorge Luiz R; Torres-Santos, Eduardo Caio; Faiões, Viviane dos S; Del Cistia, Catarina de Nigris; Sant'Anna, Carlos Maurício R; Rodrigues-Santos, Cláudio Eduardo; Echevarria, Aurea

    2015-10-20

    A series of eleven 3,4-methylenedioxyde-6-X-benzaldehyde-thiosemicarbazones (16-27) was synthesised as part of a study to search for potential new drugs with a leishmanicidal effect. The thiosemicarbazones, ten of which are new compounds, were prepared in good yields (85-98%) by the reaction of 3,4-methylenedioxyde-6-benzaldehydes (6-X-piperonal), previously synthesised for this work by several methodologies, and thiosemicarbazide in ethanol with a few drops of H2SO4. These compounds were evaluated against Leishmania amazonensis promastigotes, and derivatives where X = I (22) and X = CN (23) moieties showed impressive results, having IC₅₀ = 20.74 μM and 16.40 μM, respectively. The intracellular amastigotes assays showed IC₅₀ = 22.00 μM (22) and 17.00 μM (23), and selectivity index >5.7 and >7.4, respectively, with a lower toxicity compared to pentamidine (positive control, SI = 4.5). The results obtained from the preliminary QSAR study indicated the hydrophobicity (log P) as a fundamental parameter for the 2D-QSAR linear model. A molecular docking study demonstrated that both compounds interact with flavin mononucleotide (FMN), important binding site of NO synthase. PMID:26375353

  5. Toxic effects of bis(thiosemicarbazone) compounds and its palladium(II) complexes on herpes simplex virus growth.

    Genova, Petia; Varadinova, Tatiana; Matesanz, Ana I; Marinova, Desislava; Souza, Pilar

    2004-06-01

    Here, we present data on the activity of benzyl bis(thiosemicarbazone); 3,5-diacyl-1,2,4-triazole bis(4-methylthiosemicarbazone) and their Pd(II) complexes against the replication of wild type and of acyclovir (ACV)-resistant, herpes simplex virus type 1 (HSV 1) and type 2 (HSV 2) strains. The data were compared to those under the action of acyclovir. The testing of cytotoxic activity suggests that these compounds may be endowed with important antiviral properties. It is interesting to note that the Pd(II)-benzyl bis(thiosemicarbazone) complex, 2, exhibits a significant activity against acyclovir-resistant viruses R-100 (HSV 1) and PU (HSV 2) with an in vitro selectivity index (SI) of 8.0 vs. 0.01 for acyclovir. This complex also negatively influenced the expression of key structural HSV 1 proteins (VP23, gH and gG/gD), thus suppressing simultaneously virus entry, transactivation of virus genome, capsid assembly, and cell-to-cell spread of infectious HSV progeny. PMID:15163546

  6. Nickel(ii) radical complexes of thiosemicarbazone ligands appended by salicylidene, aminophenol and aminothiophenol moieties.

    Kochem, Amélie; Gellon, Gisèle; Jarjayes, Olivier; Philouze, Christian; du Moulinet d'Hardemare, Amaury; van Gastel, Maurice; Thomas, Fabrice

    2015-07-28

    The nickel(ii) complexes of three unsymmetrical thiosemicarbazone-based ligands featuring a sterically hindered salicylidene (1), aminophenol (2) or thiophenol (3) moiety were synthesized and structurally characterized. The metal ion lies in an almost square planar geometry in all the complexes. The cyclic voltammetry (CV) curve of 1 shows an irreversible oxidation wave at E = 0.49 V, which is assigned to the phenoxyl/phenolate redox couple. The CV curves of 2 and 3 display a reversible one-electron oxidation wave (E1/2 = 0.26 and 0.22 V vs. Fc(+)/Fc, respectively) and an one-electron reduction wave (E1/2 = -1.55 and -1.46 V, respectively). The cations 2(+) and 3(+) as well as the anions 2(-) and 3(-) were generated. The EPR spectra of the cations in THF show a rhombic signal at g1 = 2.034, g2 = 2.010 and g3 = 1.992 (2(+)) and g1 = 2.069, g2 = 2.018, g3 = 1.986 (3(+)) that is consistent with a main radical character of the complexes. The difference in anisotropy is assigned to the different nature of the radical, iminosemiquinonate vs. iminothiosemiquinonate. The anions display an isotropic EPR signal at giso = 2.003 (2(+)) and 2.006 (3(+)), which is indicative of a main α-diimine radical character of the compounds. Both the anions and cations exhibit charge transfer transitions of low to moderate intensity in their visible spectrum. Quantum chemical calculations (B3LYP) reproduce both the g-values and Vis-NIR spectra of the complexes. The radical anions readily react with dioxygen to give the radical cations. 2(+) catalyzes the aerobic oxidation of benzyl alcohol into benzaldehyde. PMID:26086684

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

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

    2015-04-01

    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, (1) H NMR and (13) C 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

  8. Potential mechanism of the anti-trypanosomal activity of organoruthenium complexes with bioactive thiosemicarbazones.

    Demoro, Bruno; Rossi, Miriam; Caruso, Francesco; Liebowitz, Daniel; Olea-Azar, Claudio; Kemmerling, Ulrike; Maya, Juan Diego; Guiset, Helena; Moreno, Virtudes; Pizzo, Chiara; Mahler, Graciela; Otero, Lucía; Gambino, Dinorah

    2013-06-01

    In the search for new metal-based drugs against diseases produced by trypanosomatid parasites, four organoruthenium(II) compounds [Ru2(p-cymene)2(L)2]X2, where L are bioactive 5-nitrofuryl-containing thiosemicarbazones and X = Cl or PF6, had been previously obtained. These compounds had shown activity on Trypanosoma brucei, the etiological agent of African trypanosomiasis. Because of genomic similarities between trypanosomatides, these ruthenium compounds were evaluated, in the current work, on Trypanosoma cruzi, the parasite responsible of American trypanosomiasis (Chagas disease). Two of them showed significant in vitro growth inhibition activity against the infective trypomastigote form of T. cruzi (Dm28c clone, IC50 = 11.69 and 59.42 μM for [Ru2(p-cymene)2(L4)2]Cl2 and [Ru2(p-cymene)2(L1)2]Cl2, respectively, where HL4 = 5-nitrofuryl-N-phenylthiosemicarbazone and HL1 = 5-nitrofurylthiosemicarbazone), showing fairly good selectivities toward trypanosomes with respect to mammalian cells (J774 murine macrophages). Moreover, [Ru2(p-cymene)2(L2)2]Cl2, where HL2 = 5-nitrofuryl-N-methylthiosemicarbazone, was synthesized in order to evaluate the effect of improved solubility on biological behavior. This new chloride salt showed higher activity against T. cruzi than that of the previously synthesized hexafluorophosphate one (Dm28c clone, IC50 = 14.30 μM for the former and 231.3 μM for the latter). In addition, the mode of antitrypanosomal action of the organoruthenium compounds was investigated. The complexes were not only able to generate toxic free radicals through bioreduction but they also interacted with two further potential parasite targets: DNA and cruzipain, a cysteine protease which plays a fundamental role in the biological cycle of these parasites. The results suggest a "multi-target" mechanism of trypanosomicidal action for the obtained complexes. PMID:23564472

  9. Structural study of two N(4)-substituted thiosemicarbazones prepared from 1-phenyl-1,2-propanedione-2-oxime and their binuclear nickel(II) complexes

    Kaminsky, Werner; Jasinski, Jerry P.; Woudenberg, Richard; Goldberg, Karen I.; West, Douglas X.

    2002-05-01

    The crystal structures of the oxime/thiosemicarbazones 1-phenyl-1-{ N(4)-methyl- and 1-phenyl-1-{ N(4)-ethylthiosemicarbazone}-2-oximepropane, H 2Po4M and H 2Po4E, were found to have the oxime and thiosemicarbazone moieties on opposite sides of the carbon-carbon backbone. Intermolecular hydrogen bonding involves the oxime function forming a symmetrical dimer for both compounds. The structures of the binuclear nickel(II) complexes, [Ni(Po4M)] 2 and [Ni(Po4E)] 2, show that bridging by the oximato N-O results in a centrosymmetric arrangement of the two planar nickel centers in each complex. The coordinated thiosemicarbazonato moieties undergo the expected changes in bond distances and angles compared to H 2Po4M and H 2Po4E.

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

    Tudor Rosu

    2013-07-01

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

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

    Bal-Demirci, Tülay; Şahin, Musa; Özyürek, Mustafa; Kondakçı, Esin; Ülküseven, Bahri

    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, 1H 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 rad OH, O2rad - and H2O2) of these compounds were also determined. All the compounds have shown encouraging ROS scavenging activities.

  12. Design and synthesis of novel 5,6-disubstituted pyridine-2,3-dione-3-thiosemicarbazone derivatives as potential anticancer agents.

    Xie, Wenlin; Xie, Shimin; Zhou, Ying; Tang, Xufu; Liu, Jian; Yang, Wenqian; Qiu, Minghua

    2014-06-23

    A series of 5,6-disubstituted pyridine-2,3-dione-3-thiosemicarbazone derivatives(2a-2n) and 5,6-disubstituted pyridine-2,3-dione S-benzyl-3-thiosemicarbazones(3a-3g) were synthesized starting from 2,3-dihydroxypyridine via oxidation-Michael additions, condensations and nucleophilic substitutions. The structures of the compounds were established by IR, (1)H NMR, (13)C NMR, and HRMS. All newly synthesized compounds were screened for their anticancer activity against Breast cancer (MCF-7), Colon cancer (HCT-116) and hepatocellular cancer (BEL7402) cell lines. Bioassay results indicated that most of the prepared compounds exhibited cytotoxicity against various cancer cells in vitro. Some of the compounds exhibited promising antiproliferative activity, which were comparable to the positive control (5-fluorouracil). The structure-activity relationship was discussed. PMID:24819956

  13. Synthèse, Caractérisation et Application dans l’Environnement d’un Nouveau Ligand, dérivé de la Thiosemicarbazone.

    BENAYAD, HOUARI

    2014-01-01

    Les travaux réalisés dans ce mémoire ont pour but de tester un ligand organique dans le but d’éliminer des métaux lourds par complexation. Le choix du ligand Thiosemicarbazone de l’imidazole-3-carboxaldéhyde été effectué vu sa structure polydentate, possédant plusieurs sites potentiels donneurs susceptible de chélater les métaux lourds dans l’eau. Les cinétiques d’adsorption étudiées sur la thiosemicarbazone de l’imidazole-3-carboxaldéhyde, montrent que ce ligand est un bon ...

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

    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

    2016-01-01

    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. (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. PMID:26583314

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

    Fatma Kandemirli

    2012-03-01

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

  16. Cytotoxic and Antitumour Studies of Acetoacetanilide N(4)-methyl(phenyl)thiosemicarbazone and its Transition Metal Complexes

    Priya, N. P.; Firdous, A. P.; Jeevana, R.; Aravindakshan, K. K.

    2015-01-01

    Cytotoxic activities of acetoacetanilide N(4)-methyl(phenyl)thiosemicarbazone (L2H) and its seven different metal complexes were studied. Of these, IC50 value of the copper complex was found to be 46 μg/ml. Antitumour studies of this copper complex was carried out using Daltons Lymphoma Ascites cell-induced solid tumour model and Ehrlich's Ascites Carcinoma cell-induced ascites tumour model. Administration of the copper complex at different concentrations (10, 5 and 1 mg/kg b. wt) inhibited the solid tumour development in mice and increased the mean survival rate and the life span of Ascites tumour bearing mice in a concentration dependent manner. PMID:26997691

  17. Spectroscopic, thermal and antibacterial studies on Mn(II and Co(II complexes derived from thiosemicarbazone

    SULEKH CHANDRA

    2009-08-01

    Full Text Available Mn(II and Co(II complexes having the general composition [M(L2X2] (where L = 2-pyridinecarboxaldehyde thiosemicarbazone, M = Mn(II and Co(II, X = Cl- and NO3- were synthesized. All the metal complexes were characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, EPR, electronic spectral studies and thermogravimetric analysis (TG. Based on the spectral studies, an octahedral geometry was assigned for all the complexes. Thermal studies of the compounds suggest that the complexes are more stable than the free ligand. This fact was supported by the kinetic parameters calculated using the Horowitz–Metzger (H–M and Coats–Redfern (C–R equations. The antibacterial properties of the ligand and its metal complexes were also examined and it was observed that the complexes are more potent bactericides than the free ligand.

  18. Spectroscopic and biological approach of Ni(II) and Cu(II) complexes of 2-pyridinecarboxaldehyde thiosemicarbazone

    Chandra, Sulekh; Raizada, Smriti; Tyagi, Monika; Sharma, Praveen Kumar

    2008-03-01

    Ni(II) and Cu(II) complexes having the general composition [M(L) 2X 2] [where L = 2-pyridinecarboxaldehyde thiosemicarbazone, M = Ni(II) and Cu(II), X = Cl -, NO 3- and 1/2 SO 42-] have been synthesized. All the metal complexes were characterized by elemental analysis, molar conductance, magnetic moment, mass, IR, EPR and electronic spectral studies. The magnetic moment measurements of the complexes indicate that all the complexes are of high-spin type. On the basis of spectral studies an octahedral geometry has been assigned for Ni(II) complexes whereas tetragonal geometry for Cu(II) except [Cu(L) 2SO 4] which posseses five coordinated geometry. The ligand and its metal complexes were screened against phytopathogenic fungi and bacteria in vitro.

  19. Cytotoxic and Antitumour Studies of Acetoacetanilide N(4)-methyl(phenyl)thiosemicarbazone and its Transition Metal Complexes.

    Priya, N P; Firdous, A P; Jeevana, R; Aravindakshan, K K

    2015-01-01

    Cytotoxic activities of acetoacetanilide N(4)-methyl(phenyl)thiosemicarbazone (L2H) and its seven different metal complexes were studied. Of these, IC50 value of the copper complex was found to be 46 μg/ml. Antitumour studies of this copper complex was carried out using Daltons Lymphoma Ascites cell-induced solid tumour model and Ehrlich's Ascites Carcinoma cell-induced ascites tumour model. Administration of the copper complex at different concentrations (10, 5 and 1 mg/kg b. wt) inhibited the solid tumour development in mice and increased the mean survival rate and the life span of Ascites tumour bearing mice in a concentration dependent manner. PMID:26997691

  20. Synthesis and evaluation of naphthalene-based thiosemicarbazone derivatives as new anticancer agents against LNCaP prostate cancer cells.

    Altintop, Mehlika Dilek; Sever, Belgin; Özdemir, Ahmet; Kuş, Gökhan; Oztopcu-Vatan, Pinar; Kabadere, Selda; Kaplancikli, Zafer Asim

    2016-06-01

    Fourteen new naphthalene-based thiosemicarbazone derivatives were designed as anticancer agents against LNCaP human prostate cancer cells and synthesized. MTT assay indicated that compounds 6, 8 and 11 exhibited inhibitory effect on LNCaP cells. Among these compounds, 4-(naphthalen-1-yl)-1-[1-(4-hydroxyphenyl)ethylidene)thiosemicarbazide (6), which caused more than 50% death on LNCaP cells, was chosen for flow cytometric analysis of apoptosis. Flow cytometric analysis pointed out that compound 6 also showed apoptotic effect on LNCaP cells. Compound 6 can be considered as a promising anticancer agent against LNCaP cells owing to its potent cytotoxic activity and apoptotic effect. PMID:25826149

  1. Simultaneous spectrophotometric determination of molybdenum and iron with salicylaldehyde thiosemicarbazone, and application to the analysis of steels

    Salicylaldehyde thiosemicarbazone reacts with molybdenum(VI) in mineral acid solution, in the presence of stannous chloride, to produce a 1:1 red-violet complex (lambdasub(max)=520 nm, epsilon=4.8x103 l.mole-1.cm-1). Iron (II and III) forms a green 1:2 complex, in ammonia-ammonium chloride solution (lambdasub(max)=590 nm, epsilon=1.7x103 l.mole-1.cm-1). Both complexes have been used with success in the photometric estimation of molybdenum and iron in mixtures. Molybdenum may be determined in presence of 40 times its weight of iron. Iron may be determined in presence of twice its weight of molybdenum. The reagent can be applied to the analysis of steels. The interferences of some metallic ions have been examined

  2. Radiosynthesis and evaluation of [{sup 61}Cu]-9,10-phenanthrenequinone thiosemicarbazone in fibrosarcoma-bearing animals for PET imaging

    Jalilian, A.R.; Akhlaghi, M.; Kamali-Dehghan, M.; Shafaii, K.; Moradkhani, S. [Agricultural, Medical and Industrial Research School (AMIRS-NSTRI), Karaj (Iran); Emami, A. [Islamic Azad University, Tehran (Iran). Pharmaceutical Sciences Branch

    2010-07-01

    [{sup 61}Cu]-9,10-Phenanthrenequinone thiosemicarbazone ({sup 61}Cu-PQTS), a radiolabeled anticancer compound was prepared for malignant tissue imaging studies. Copper-61 was produced via the {sup nat}Zn(p, x){sup 61}Cu nuclear reaction in a 30 MeV cyclotron (150 {mu}A irradiation for 76 min, radionuclidic purity >95%). {sup 61}Cu-PQTS was prepared from in-house synthesized PQTS. Quality control was performed using ITLC. The biodistribution of the tracer was compared to the biodistribution of cationic copper-61 in healthy controls. {sup 61}Cu-PQTS was then administered to fibrosarcoma-bearing mice for biodistribution and co-incidence imaging studies. {sup 61}Cu-PQTS demonstrated significant tumor uptake of 2.1% ID/g and the tumor was clearly visualized in a fibrosarcoma model. (orig.)

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

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

  4. Radiosynthesis and evaluation of [61Cu]-9,10-phenanthrenequinone thiosemicarbazone in fibrosarcoma-bearing animals for PET imaging

    [61Cu]-9,10-Phenanthrenequinone thiosemicarbazone (61Cu-PQTS), a radiolabeled anticancer compound was prepared for malignant tissue imaging studies. Copper-61 was produced via the natZn(p, x)61Cu nuclear reaction in a 30 MeV cyclotron (150 μA irradiation for 76 min, radionuclidic purity >95%). 61Cu-PQTS was prepared from in-house synthesized PQTS. Quality control was performed using ITLC. The biodistribution of the tracer was compared to the biodistribution of cationic copper-61 in healthy controls. 61Cu-PQTS was then administered to fibrosarcoma-bearing mice for biodistribution and co-incidence imaging studies. 61Cu-PQTS demonstrated significant tumor uptake of 2.1% ID/g and the tumor was clearly visualized in a fibrosarcoma model. (orig.)

  5. Spectroscopic, viscositic and molecular modeling studies on the interaction of 3'-azido-daunorubicin thiosemicarbazone with DNA.

    Cui, Fengling; Liu, Qingfeng; Luo, Hongxia; Zhang, Guisheng

    2014-01-01

    A new daunorubicin has been synthesized and structurally characterized. The interaction of native calf thymus DNA (ctDNA) with 3'-azido-daunorubicin thiosemicarbazone (ADNRT) was investigated under simulated physiological conditions by multi-spectroscopic techniques, viscometric measurements and molecular modeling study. It concluded that ADNRT could intercalate into the base pairs of ctDNA, and the fluorescence quenching by ctDNA was static quenching type. Thermodynamic parameters calculated suggested that the binding of ADNRT to ctDNA was mainly driven by hydrophobic interactions. The relative viscosity of ctDNA increased with the addition of ADNRT, which confirmed the intercalation mode. Furthermore, molecular modeling studies corroborate the above experimental results. PMID:23974700

  6. Spectrophotometric determination of micro-amounts of ruthenium(III) and platinum(IV) with acenaphthenequinone mono(thiosemicarbazone)

    Ruthenium(III) and platinum(IV) form 1:2 (metal:ligand) complexes with acenaphthenequinone mono(thiosemicarbazone)(AQTS). The complexes are soluble in 70 % N,N-dimethylformamide (DMF). The reagent has been used for the spectrophotometric determination of Ru(III) and Pt(IV). The optimum ranges of concentration for the determination of Ru(III) and Pt(IV) are 2.02 - 7.09 and 2.83 - 11.6 ppm over the pH range 5.3 - 6.8 and 1.9 - 4.1, respectively. The Sandell sensitivities for the determination of Ru(III) and Pt(IV) are 0.01 and 0.016 μg cm-2, respectively. The determination has also been carried out in the presence of foreign ions. (author)

  7. Spectrophotometric determination of micro-amounts of ruthenium(III) and platinum(IV) with acenaphthenequinone mono(thiosemicarbazone)

    Singh, S.K.; Sharma, R.K.; Sindhwani, S.K.

    1986-04-01

    Ruthenium(III) and platinum(IV) form 1:2 (metal:ligand) complexes with acenaphthenequinone mono(thiosemicarbazone) (AQTS). The complexes are soluble in 70% N,N-dimethylformamide (DMF). The reagent has been used for the spectrophotometric determination of Ru(III) and Pt(IV). The optimum ranges of concentration for the determination of Ru(III) and Pt(IV) are 2.02 - 7.09 and 2.83 - 11.6 ppm over the pH range 5.3 - 6.8 and 1.9 - 4.1, respectively. The Sandell sensitivities for the determination of Ru(III) and Pt(IV) are 0.01 and 0.016 ..mu..g cm/sup -2/, respectively. The determination has also been carried out in the presence of foreign ions.

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

    Chandra, Sulekh; Kumar, Anil

    2007-12-01

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

  9. comparative analysis of cellular respiratory inhibition by substituted phenylglyoxal-bis-(4-methyl-3-thiosemicarbazone) zinc chelates.

    Coats, E A; Milstein, S R; Pleiss, M A; Roesener, J A; Schmidt, J; McDonald, J; Reed, R

    1983-03-01

    Fourteen para-substituted phenylglyoxal-bis-(4-methyl-3-thiosemicarbazone) zinc chelates have been synthesized as inhibitors of cellular respiration and therefore as potential antineoplastic agents. Each chelate has been evaluated as an inhibitor of Ehrlich ascites tumor cell and of rat liver slice respiration. The molar I50 values for respiratory inhibition have been subjected to computerized correlation to delineate quantitative relationships between biological activity and chemical structure. Activity against the tumor cell model is characterized by a positive lipophilic and a detrimental steric influence while activity against rat liver slice displays only a weak positive lipophilic effect. Quantitative comparative analysis suggests that selective action against the tumor cell system can be improved by substituents which are electron withdrawing and lipophilic in nature. PMID:6852227

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

    Hatem E. Gaffer

    2015-12-01

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

  11. Thermodynamics of the complexation between salicylaldehyde thiosemicarbazone with Cu2+ ion in methanol +1,4-dioxane binary solutions

    Biswas Rashmidipta

    2014-01-01

    Full Text Available The complexation reaction between salicylaldehyde thiosemicarbazone, abbreviated as STSC, with Cu2+ ion was studied in the binary mixtures of methanol + 1,4-dioxane binary by using UV-Visible spectrophotometric and conductometric methods at different temperatures. The formation constants (Kf for the 1:1 complex, Cu2+-STSC, were calculated from computer fitting of the absorbance and molar conductance data against various mole ratios (cM:cL or cL:cM in different binary solvent mixtures. A non-linear correlation was observed for the variation of logKf for the complex against the solvent compositions. Various thermodynamic parameters (ΔH, ΔS and ΔG for the formation of Cu2+-STSC complex were also determined from the temperature dependence of the stability constants (Kf. The results showed that the complexation reaction is affected by the nature and composition of the mixed solvents.

  12. SYNTHESIS, STRUCTURE AND BIOLOGICAL ACTIVITY OF N(4-ALLYL-3-THIOSEMICARBAZONES AND THEIR COORDINATION COMPOUNDS WITH SOME 3D METALS

    Vasilii GRAUR

    2016-02-01

    Full Text Available The paper presents a review of different N(4-allyl-3-thiosemicarbazones and their coordination compounds described in literature. N(4-allyl-3-thiosemicarbazide can form corresponding thiosemicarbazones with aliphatic, aromatic and heteroaromatic carbonyl compounds. In the presence of transitional metal ions they can form coordination compounds of different structures. Both coordination compounds and proligands manifest antitumor, antibacterial, antiviral, and antimalarial activities. Copper(II coordination compounds with these ligands manifest better antitumor activity than corresponding proligands. SINTEZA, STRUCTURA ŞI ACTIVITATEA BIOLOGICĂ A N(4-ALIL-3-TIOSEMICARBAZONELOR ŞI A COMPUŞILOR COORDINATIVI AI UNOR METALE 3D CU ACEŞTI LIGANZILucrarea prezintă o revistă a N(4-alil-3-tiosemicarbazonelor şi a compuşilor coordinativi cu aceşti liganzi descrise în literatura de specialitate. N(4-alil-3-tiosemicarbazida formează tiosemicarbazone cu aldehide şi cetone alifatice, aro­matice şi heteroaromatice. În prezenţa ionilor de metale de tranziţie acestea pot forma compuşi coordinativi cu diferite structuri. N(4-alil-3-tiosemicarbazonele şi compuşii coordinativi manifestă activitate antitumorală, antibacterială, antivirală şi antimalarică. Compuşii coordinativi ai cuprului cu aceşti liganzi manifestă activitate antitumorală sporită în comparaţie cu N(4-alil-3-tiosemicarbazonele corespunzătoare. 

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

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

    2011-01-01

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

  14. Ribonucleotide reductase inhibition by metal complexes of Triapine (3-aminopyridine-2-carboxaldehyde thiosemicarbazone): A combined experimental and theoretical study

    Popović-Bijelić, Ana; Kowol, Christian R.; Lind, Maria E.S.; Luo, Jinghui; Himo, Fahmi; Enyedy, Éva A.; Arion, Vladimir B.; Gräslund, Astrid

    2012-01-01

    Triapine (3-aminopyridine-2-carboxaldehyde thiosemicarbazone, 3-AP) is currently the most promising chemotherapeutic compound among the class of α-N-heterocyclic thiosemicarbazones. Here we report further insights into the mechanism(s) of anticancer drug activity and inhibition of mouse ribonucleotide reductase (RNR) by Triapine. In addition to the metal-free ligand, its iron(III), gallium(III), zinc(II) and copper (II) complexes were studied, aiming to correlate their cytotoxic activities with their effects on the diferric/tyrosyl radical center of the RNR enzyme in vitro. In this study we propose for the first time a potential specific binding pocket for Triapine on the surface of the mouse R2 RNR protein. In our mechanistic model, interaction with Triapine results in the labilization of the diferric center in the R2 protein. Subsequently the Triapine molecules act as iron chelators. In the absence of external reductants, and in presence of the mouse R2 RNR protein, catalytic amounts of the iron(III)–Triapine are reduced to the iron(II)–Triapine complex. In the presence of an external reductant (dithiothreitol), stoichiometric amounts of the potently reactive iron (II)–Triapine complex are formed. Formation of the iron(II)–Triapine complex, as the essential part of the reaction outcome, promotes further reactions with molecular oxygen, which give rise to reactive oxygen species (ROS) and thereby damage the RNR enzyme. Triapine affects the diferric center of the mouse R2 protein and, unlike hydroxyurea, is not a potent reductant, not likely to act directly on the tyrosyl radical. PMID:21955844

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

    Introduction: The pyruvaldehyde bis(N4-methylthiosemicarbazonato)copper(II) (Cu-PTSM) and diacetyl bis(N4-methylthiosemicarbazonato)copper(II) (Cu-ATSM) radiopharmaceuticals exhibit strong, species-dependent binding to the IIA site of human serum albumin (HSA), while the related ethylglyoxal bis(thiosemicarbazonato)copper(II) (Cu-ETS) radiopharmaceutical appears to exhibit only nonspecific binding to HSA and animal serum albumins. Methods: To further probe the structural basis for the species dependence of this albumin binding interaction, we examined protein binding of these three radiopharmaceuticals in solutions of albumin and/or serum from a broader array of mammalian species (rat, sheep, donkey, rabbit, cow, pig, dog, baboon, mouse, cat and elephant). We also evaluated the albumin binding of several copper(II) bis(thiosemicarbazone) chelates offering more diverse substitution of the ligand backbone. Results: Cu-PTSM and Cu-ATSM exhibit a strong interaction with HSA that is not apparent with the albumins of other species, while the binding of Cu-ETS to albumin is much less species dependent. The strong interaction of Cu-PTSM with HSA does not appear to simply correlate with variation, relative to the animal albumins, of a single amino acid lining HSA's IIA site. Those agents that selectively interact with HSA share the common feature of only methyl or hydrogen substitution at the carbon atoms of the diimine fragment of the ligand backbone. Conclusions: The interspecies variations in albumin binding of Cu-PTSM and Cu-ATSM are not simply explained by unique amino acid substitutions in the IIA binding pocket of the serum albumins. However, the specific affinity for this region of HSA is disrupted when substituents bulkier than a methyl group appear on the imine carbons of the copper bis(thiosemicarbazone) chelate.

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

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

    2009-07-15

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

  17. Antioxidant, antimicrobial, and theoretical studies of the thiosemicarbazone derivative Schiff base 2-(2-imino-1-methylimidazolidin-4-ylidene)hydrazinecarbothioamide (IMHC)

    Al-Amiery, Ahmed A.; Al-Majedy, Yasmien K; Ibrahim, Heba H; Al-Tamimi, Ali A

    2012-01-01

    Background Adverse antimicrobial activities of thiosemicarbazone (TSC) and Schiff base derivatives have widely been studied by using different kinds of microbes, in addition different methods were used to assay the antioxidant activities using DPPH, peroxids, or ntrosyl methods. However, there are no studies describing the synthesis of TSC derived from creatinine. Results In this study, 2-(2-imino-1-methylimidazolidin-4-ylidene)hydrazinecarbothioamide (IMHC) was synthesized by the reaction of...

  18. Synthesis, X-ray structure and in vitro cytotoxicity studies of Cu(I/II) complexes of thiosemicarbazone: special emphasis on their interactions with DNA.

    Saswati; Chakraborty, Ayon; Dash, Subhashree P; Panda, Alok K; Acharyya, Rama; Biswas, Ashis; Mukhopadhyay, Subhadip; Bhutia, Sujit K; Crochet, Aurélien; Patil, Yogesh P; Nethaji, M; Dinda, Rupam

    2015-04-01

    4-(p-X-phenyl)thiosemicarbazone of napthaldehyde {where X = Cl (HL¹) and X = Br (HL²)}, thiosemicarbazone of quinoline-2-carbaldehyde (HL³) and 4-(p-fluorophenyl)thiosemicarbazone of salicylaldehyde (H₂L⁴) and their copper(I) {[Cu(HL¹)(PPh₃)₂Br]·CH₃CN (1) and [Cu(HL²)(PPh₃)₂Cl]·DMSO (2)} and copper(II) {[(Cu₂L³₂Cl)₂(μ-Cl)₂]·2H₂O (3) and [Cu(L⁴)(Py)] (4)} complexes are reported herein. The synthesized ligands and their copper complexes were successfully characterized by elemental analysis, cyclic voltammetry, NMR, ESI-MS, IR and UV-Vis spectroscopy. Molecular structures of all the Cu(I) and Cu(II) complexes have been determined by X-ray crystallography. All the complexes (1-4) were tested for their ability to exhibit DNA-binding and -cleavage activity. The complexes effectively interact with CT-DNA possibly by groove binding mode, with binding constants ranging from 10⁴ to 10⁵ M⁻¹. Among the complexes, 3 shows the highest chemical (60%) as well as photo-induced (80%) DNA cleavage activity against pUC19 DNA. Finally, the in vitro antiproliferative activity of all the complexes was assayed against the HeLa cell line. Some of the complexes have proved to be as active as the clinical referred drugs, and the greater potency of 3 may be correlated with its aqueous solubility and the presence of the quinonoidal group in the thiosemicarbazone ligand coordinated to the metal. PMID:25736331

  19. Novel platinum(II) and palladium(II) complexes of thiosemicarbazones derived from 5-substitutedthiophene-2-carboxaldehydes and their antiviral and cytotoxic activities

    Karaküçük-İyidoğan, Ayşegül; Taşdemir, Demet; Oruç-Emre, Emine Elçin; Balzarini, Jan

    2011-01-01

    A series of thiosemicarbazones and their platinum(II) and palladium(II) complexes have been synthesized. The chemical structures of ligands and their complexes were characterized by UV-Vis, IR, (1)H NMR, (13)C NMR, MS spectra, elemental analysis and TGA. The antiviral and cytotoxic activities of all compounds have been tested. Results of broad antiviral evaluation showed that none of the compounds evaluated endowed with anti-DNA or -RNA virus activity at subtoxic concentrations except for the...

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

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

    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 sing...

  1. Synthesis, Spectral, and Biological Properties of Copper(II) Complexes of Thiosemicarbazones of Schiff Bases Derived from 4-Aminoantipyrine and Aromatic Aldehydes

    2006-01-01

    We have synthesized a novel series of Schiff bases by condensation of 4-aminoantipyrine and various aromatic aldehydes followed by reaction with thiosemicarbazide. These thiosemicarbazones are potential ligands toward transition metal ions. The reaction of copper(II) salts with 4[N-(benzalidene)amino]antipyrinethiosemicarbazone (BAAPTS), 4[N-(4′-methoxybenzalidene) amino] antipyrinethiosemicarbozone (MBAAPTS), 4[N-(4′-dimethylamino benzalidene) amino] antipyrinethiosemicarbazone (DA...

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

    Serda, Maciej; Kalinowski, Danuta S.; Rasko, Nathalie; Potůčková, Eliška; Mrozek-Wilczkiewicz, Anna; Musiol, Robert; Jan G Małecki; 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...

  3. Iron and Cobalt Complexes of 2,6-Diacetylpyridine-bis(R-thiosemicarbazone) (R=H, phenyl) Showing Unprecedented Ligand Deviation from Planarity

    Panja, Anangamohan; Campana, Charles; Leavitt, Christopher; van Stipdonk, Michael J.; Eichhorn, David M.

    2009-01-01

    The syntheses, characterization, and single-crystal X-ray crystal structures are reported for four complexes of iron and cobalt with the pentadentate ligands, 2,6-diacetylpyridinebis(thiosemicarbazone) (H2L1) and 2,6-diacetylpyridinebis-(phenylthiosemicarbazone) (H2L2), including a cobalt dimer displaying a deviation from planarity which is unprecedented for this class of ligands and allows the ligand to occupy five positions of a pseudo-octahedral coordination sphere. This dimer reacts with ...

  4. Determination of Ni(II) with picolinaldehyde-4-phenyl-3-thiosemicarbazone used as a chromogenic reagent in a nonionic micellar system

    BALOUCH, Aamna; BHANGER, Muhammad Iqbal; TALPUR, Farah Naz

    2011-01-01

    Spectrophotometric determination of Ni(II) was carried out using picolinaldehyde-4-phenyl-3-thiosemicarbazone (PAPT) as a complexing/chromogenic reagent. The possibility of using a micellar system was explored to enhance the degree of detection and allow a more sensitive spectrophotometric method for the determination of nickel ions. The anionic surfactant Triton X-100 greatly enhanced the molar absorptivity and limit of detection relative to that observed with bulk water or an organ...

  5. Structure and bonding of some newly synthesized complexes of lanthanide(III) complexes of 4[N-(p-dimetaylaminobenzalidene) amino] antipyrine thiosemicarbazone

    A series of complexes of the type LnX3.2(DABAAPTS), where Ln = La, Pr, Nd, Sm, Gd, Tb, Dy and Ho, X = ClO4-, or NCS-, DABAAPTS=4[N- (p-dimethylaminobenzalidene) amino] anti pyrine thiosemicarbazone have been synthesized and characterized on the basis of elemental analysis, molecular weight measurements, molar conductance, room temperature magnetic moment, infrared and electronic spectral data. The ligand DABAAPTS behaves as neutral tridentate (N2S) ligand. (author)

  6. Some observations on the use of 2-hydroxyacetophenone thiosemicarbazone as a spectrophotometric reagent for the determination of vanadium(IV) and vanadium(V)

    2-hydroxyacetophenone thiosemicarbazone produce pale yellow coloured solutions with vanadium(IV) and vanadium(V) in acetic acid-sodium acetate buffer medium. The colour obtained has been used to develop spectrophotometric methods for the determination of vanadium(IV) and vanadium(V) in the concentration ranges 1.02-4.59 ppm and 0.2-4.6 ppm λmax 360nm) respectively. (author). 9 refs., 3 tabs

  7. QSAR study of some 5-methyl/trifluoromethoxy- 1H-indole-2,3-dione-3-thiosemicarbazone derivatives as anti-tubercular agents

    Shahlaei, M.; Fassihi, A.; Nezami, A.

    2009-01-01

    In the present study, quantitative relationships between molecular structure and anti-tubercular activity of some 5-methyl/trifluoromethoxy-1H-indole-2,3-dione-3-thiosemicarbazone derivatives were discovered. The detailed application of an efficient linear method and principal component regression (PCR) for the evaluation of quantitative structure activity relationships of the studied compounds is demonstrated. Components produced by principal component analysis were used as the input for a l...

  8. Evaluation of the Influence of thiosemicarbazone-triazole hybrids on genes implicated in lipid oxidation and accumulation as potential anti-obesity agents.

    Kinfe, Henok H; Belay, Yonas H; Joseph, Jitcy S; Mukwevho, Emmanuel

    2013-10-01

    A series of thiosemicarbazone-triazole hybrids 1a-h are efficiently synthesised and evaluated for their influence on the expression of genes, cpt-1, acc-1 and pgc-1, which are essential in lipid metabolism. The test results show that hybrids 1c and 1g exhibited relatively high influence on the expression of cpt-1 and pgc-1 and suppression of acc-1 as desired. PMID:23988353

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

    Lakshmi Narayana Suvarapu; Sung-Ok Baek

    2015-01-01

    A chelating agent, 4-benzyloxybenzaldehyde-4-methyl-3-thiosemicarbazone (BBMTSC), containing sulphur and nitrogen donor atoms was synthesized and applied as a ligand for the chelation of Cd(II). Both the BBMTSC and its Cd(II) complex were characterized by elemental analysis, UV-Vis absorption spectra, Fourier transform infrared spectroscopy (FT-IR), mass spectra, nuclear magnetic resonance spectroscopy (NMR), X-ray powder diffraction (XRD), and field emission scanning electron microscopy (FES...

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

    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. PMID:25147149

  11. Tricarbonyl (99m)Tc(i) and Re(i)-thiosemicarbazone complexes: synthesis, characterization and biological evaluation for targeting bacterial infection.

    Nayak, Dipak Kumar; Baishya, Rinku; Natarajan, Ramalingam; Sen, Tuhinadri; Debnath, Mita Chatterjee

    2015-09-28

    Methyl, ethyl and phenyl nitrofuryl thiosemicarbazone ligands (, and respectively) were radiolabeled with freshly prepared aqueous solution of a fac[(99m)Tc(CO)3(H2O)3](+) precursor. The radiochemical yield was around 98% as determined by thin layer chromatography and HPLC. The complexes exhibited substantial stability. The corresponding Re(i) complexes were prepared from a Re(CO)5Br precursor to understand the coordination behavior of the ligands against a tricarbonyl rhenium(i) precursor. The rhenium(i) complexes were characterized by means of IR, NMR and mass spectroscopic studies as well as by X-ray crystallography, and correlated with the technetium complexes by means of HPLC studies. Electrochemical reduction of monomeric Re(CO)3-complexes of nitrofuryl ethyl thiosemicarbazone was also studied using cyclic voltammetry. Biodistribution studies of (99m)Tc(CO)3-labeled thiosemicarbazones in rats intramuscularly infected with S. aureus exhibited substantial in vivo stability of the complex and moderate accumulation at the site of focal infection. PMID:26289802

  12. Synthesis, Spectroscopic and Physicochemical Characterization and Biological Activity of Co(II and Ni(II Coordination Compounds with 4-Aminoantipyrine Thiosemicarbazone

    Ram K. Agarwal

    2004-01-01

    Full Text Available We describe the synthesis and characterization of cobalt(II and nickel(II coordination compounds of 4[N-(furan-2’-aldimineamino]antipyrine thiosemicarbazone (FFAAPTS and 4[N-(4'-nitrobenzalidene amino]antipyrine thiosemicarbazone (4'-NO2BAAPTS. All the isolated compounds have the general composition MX2(L(H2O (M = Co2+ or Ni2+; X = Cl, Br, NO3, NCS or CH3COO; L = FFAAPTS or 4'-NO2BAAPTS and M(ClO42(L2 (M = Co2+ or Ni2+; L = FFAAPTS or 4'-NO2BAAPTS. Infrared spectral studies indicate that both the thiosemicarbazones coordinate in their neutral form and they act as {N,N,S} tridentate chelating ligands. Room temperature magnetic measurements and electronic spectral studies suggest the distorted octahedral geometries of the prepared complexes. Thermogravimetric studies are also reported and the possible structures of the complexes are proposed. Antibacterial and antifungal properties of these metal-coordination compounds have also been studied.

  13. Synthesis of a sugar-based thiosemicarbazone series and structure-activity relationship versus the parasite cysteine proteases rhodesain, cruzain, and Schistosoma mansoni cathepsin B1.

    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; Sales Júnior, Policarpo Ademar; Romanha, Alvaro José; Murta, Silvane Maria Fonseca; McKerrow, James H; Caffrey, Conor R; de Oliveira, Renata Barbosa; Ferreira, Rafaela Salgado

    2015-05-01

    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

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

    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.

  15. Synthesis, Characterization, and In Vitro Cytotoxic Activities of Benzaldehyde Thiosemicarbazone Derivatives and Their Palladium (II) and Platinum (II) Complexes against Various Human Tumor Cell Lines

    Hernándeza, Wilfredo; Paz, Juan; Vaisberg, Abraham; Spodine, Evgenia; Richter, Rainer; Beyer, Lothar

    2008-01-01

    The palladium (II) bis-chelate Pd (L1−3)2 and platinum (II) tetranuclear Pt4(L4)4 complexes of benzaldehyde thiosemicarbazone derivatives have been synthesized, and characterized by elemental analysis and IR, FAB(+)-mass and NMR (1H, 13C) spectroscopy. The complex Pd(L2)2 [HL2 = m-CN-benzaldehyde thiosemicarbazone] shows a square-planar geometry with two deprotonated ligands (L) coordinated to PdII through the nitrogen and sulphur atoms in a transarrangement, while the complex Pt4(L4)4 [HL4 = 4-phenyl-1-benzaldehyde thiosemicarbazone] has a tetranuclear geometry with four tridentate ligands coordinated to four PtII ions through the carbon (aromatic ring), nitrogen, and sulphur atoms where the ligands are deprotonated at the NH group. The in vitro antitumor activity of the ligands and their complexes was determined against different human tumor cell lines, which revealed that the palladium (II) and platinum (II) complexes are more cytotoxic than their ligands with IC50 values at the range of 0.07–3.67 μM. The tetranuclear complex Pt4(L4)4, with the phenyl group in the terminal amine of the ligand, showed higher antiproliferative activity (CI50 = 0.07–0.12 μM) than the other tested palladium (II) complexes. PMID:19148285

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

    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

    2013-08-01

    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. PMID:23829568

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

    Arumugam Manimaran

    2012-07-01

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

  18. Investigation into {sup 64}Cu-labeled Bis(selenosemicarbazone) and Bis(thiosemicarbazone) complexes as hypoxia imaging agents

    McQuade, Paul [Mallinckrodt Institute of Radiology, Washington University School of Medicine, St. Louis, MO 63110 (United States); Martin, Katherine E. [Biosciences Department, University of Kent, Canterbury CT2 7NJ (United Kingdom); Castle, Thomas C. [Biosciences Department, University of Kent, Canterbury CT2 7NJ (United Kingdom); Went, Michael J. [Biosciences Department, University of Kent, Canterbury CT2 7NJ (United Kingdom); Blower, Philip J. [Biosciences Department, University of Kent, Canterbury CT2 7NJ (United Kingdom); Welch, Michael J. [Mallinckrodt Institute of Radiology, Washington University School of Medicine, St. Louis, MO 63110 (United States); Alvin J. Siteman Cancer Center, Washington University School of Medicine, St. Louis, MO 63110 (United States); Lewis, Jason S. [Mallinckrodt Institute of Radiology, Washington University School of Medicine, St. Louis, MO 63110 (United States); Alvin J. Siteman Cancer Center, Washington University School of Medicine, St. Louis, MO 63110 (United States)]. E-mail: j.s.lewis@wustl.edu

    2005-02-01

    Background: Cu-diacetyl-bis(N{sup 4}-methylthiosemicarbazone) [Cu-ATSM], although excellent for oncology applications, may not be suitable for delineating cardiovascular or neurological hypoxia. For this reason, new Cu hypoxia positron emission tomography (PET) imaging agents are being examined to search for a higher selectivity for hypoxic or ischemic tissue at higher oxygen concentrations found in these tissues. Two approaches are to increase alkylation or to replace the sulfur atoms with selenium, resulting in the formation of selenosemicarbazones. Methods: Three {sup 64}Cu-labeled selenosemicarbazone complexes were synthesized and one was screened for hypoxia selectivity in vitro using EMT-6 mouse mammary carcinoma cells. Rodent biodistribution and small animal PET images were obtained from BALB/c mice implanted with EMT-6 tumors. One alkylated thiosemicarbazone was synthesized and examined. Results: Of the three bis(selenosemicarbazone) ligands synthesized and examined, only {sup 64}Cu-diacetyl-bis(selenosemicarbazone) [{sup 64}Cu-ASSM] was isolated in high-enough radiochemical purity to undertake cell uptake experiments where uptake was shown to be independent of oxygen concentration. The bis(thiosemicarbazone) complex synthesized, {sup 64}Cu-diacetyl-bis(N{sup 4}-ethylthiosemicarbazone) [{sup 64}Cu-ATSE], showed hypoxia selectivity similar to {sup 64}Cu-ATSM although at a higher oxygen concentration. Biodistribution studies for {sup 64}Cu-ASSM and {sup 64}Cu-ATSE showed high tumor uptake at 20 min ({sup 64}Cu-ASSM, 10.33{+-}0.78% ID/g; {sup 64}Cu-ATSE, 7.71{+-}0.46% ID/g). PET images of EMT-6 tumor-bearing mice visualized the tumor with {sup 64}Cu-ATSE and revealed hypoxia selectivity consistent with the in vitro data. Conclusion: Of the compounds synthesized, only {sup 64}Cu-ASSM and {sup 64}Cu-ATSE could be examined in vitro and in vivo. Although the stability of bis(selenosemicarbazone) complexes increased upon addition of methyl groups to the diimine

  19. Investigation into 64Cu-labeled Bis(selenosemicarbazone) and Bis(thiosemicarbazone) complexes as hypoxia imaging agents

    Background: Cu-diacetyl-bis(N4-methylthiosemicarbazone) [Cu-ATSM], although excellent for oncology applications, may not be suitable for delineating cardiovascular or neurological hypoxia. For this reason, new Cu hypoxia positron emission tomography (PET) imaging agents are being examined to search for a higher selectivity for hypoxic or ischemic tissue at higher oxygen concentrations found in these tissues. Two approaches are to increase alkylation or to replace the sulfur atoms with selenium, resulting in the formation of selenosemicarbazones. Methods: Three 64Cu-labeled selenosemicarbazone complexes were synthesized and one was screened for hypoxia selectivity in vitro using EMT-6 mouse mammary carcinoma cells. Rodent biodistribution and small animal PET images were obtained from BALB/c mice implanted with EMT-6 tumors. One alkylated thiosemicarbazone was synthesized and examined. Results: Of the three bis(selenosemicarbazone) ligands synthesized and examined, only 64Cu-diacetyl-bis(selenosemicarbazone) [64Cu-ASSM] was isolated in high-enough radiochemical purity to undertake cell uptake experiments where uptake was shown to be independent of oxygen concentration. The bis(thiosemicarbazone) complex synthesized, 64Cu-diacetyl-bis(N4-ethylthiosemicarbazone) [64Cu-ATSE], showed hypoxia selectivity similar to 64Cu-ATSM although at a higher oxygen concentration. Biodistribution studies for 64Cu-ASSM and 64Cu-ATSE showed high tumor uptake at 20 min (64Cu-ASSM, 10.33±0.78% ID/g; 64Cu-ATSE, 7.71±0.46% ID/g). PET images of EMT-6 tumor-bearing mice visualized the tumor with 64Cu-ATSE and revealed hypoxia selectivity consistent with the in vitro data. Conclusion: Of the compounds synthesized, only 64Cu-ASSM and 64Cu-ATSE could be examined in vitro and in vivo. Although the stability of bis(selenosemicarbazone) complexes increased upon addition of methyl groups to the diimine backbone, the fully alkylated species, 64Cu-ASSM, demonstrated no hypoxia selectivity. However

  20. Spectroscopic and biological approach of Ni(II), Cu(II) and Co(II) complexes of 4-methoxy/ethoxybenzaldehyde thiosemicarbazone glyoxime.

    Babahan, Ilknur; Eyduran, Fatih; Coban, Esin Poyrazoglu; Orhan, Nil; Kazar, Didem; Biyik, Halil

    2014-01-01

    Two novel vicinal dioxime ligands containing (4-methoxybenzaldehyde thiosemicarbazone glyoxime (L(1)H2) or 4-ethoxybenzaldehyde thiosemicarbazone glyoxime (L(2)H2)) thiosemicarbazone units were synthesized and characterized using (1)H NMR, (13)C NMR, HMQC, MS, infrared and, UV-VIS. spectroscopy, elemental analysis, and magnetic susceptibility measurements. Mononuclear nickel(II), copper(II) and cobalt(II) complexes with a metal:ligand ratio of 1:2 for L(1)H2 and L(2)H2 were also synthesized. The effect of pH and solvent on the absorption spectra of both ligands and complexes was determined. IR spectra show that the ligands act in a bidentate manner and coordinates N4 donor groups of the ligands to Ni(II), Cu(II) and Co(II) ions. The detection of H-bonding (O-H⋯O) in the [M(LH)2] metal complexes by IR spectra supported the square-planar MN4 coordination of mononuclear complexes. The antimicrobial activities of compounds L(1)H2, L(2)H2, and their Ni(II), Cu(II) and Co(II) complexes were evaluated using the disc diffusion method against 12 bacteria and 4 yeasts. The minimal inhibitory concentrations (MICs) against 7 bacteria and 3 yeasts were also determined. Among the test compounds attempted, L(1)H2, [Ni(L1H)2], [Cu(L1H)2], L2H2, [Ni(L2H)2] and [Cu(L2H)2] showed some activities against certain Gram-positive bacteria and some of the yeasts tested. PMID:24239764

  1. Synthesis, Characterization, and In Vitro Cytotoxic Activities of Benzaldehyde Thiosemicarbazone Derivatives and Their Palladium (II and Platinum (II Complexes against Various Human Tumor Cell Lines

    Lothar Beyer

    2009-01-01

    Full Text Available The palladium (II bis-chelate Pd (L1−32 and platinum (II tetranuclear Pt4(L44 complexes of benzaldehyde thiosemicarbazone derivatives have been synthesized, and characterized by elemental analysis and IR, FAB(+-mass and NMR (1H,13C spectroscopy. The complex Pd(L22 [HL2=m-CN-benzaldehyde thiosemicarbazone] shows a square-planar geometry with two deprotonated ligands (L coordinated to PdII through the nitrogen and sulphur atoms in a transarrangement, while the complex Pt4(L44 [HL4=4-phenyl-1-benzaldehyde thiosemicarbazone] has a tetranuclear geometry with four tridentate ligands coordinated to four PtII ions through the carbon (aromatic ring, nitrogen, and sulphur atoms where the ligands are deprotonated at the NH group. The in vitro antitumor activity of the ligands and their complexes was determined against different human tumor cell lines, which revealed that the palladium (II and platinum (II complexes are more cytotoxic than their ligands with IC50 values at the range of 0.07–3.67 μM. The tetranuclear complex Pt4(L44, with the phenyl group in the terminal amine of the ligand, showed higher antiproliferative activity (CI50 = 0.07–0.12 μM than the other tested palladium (II complexes.

  2. 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.

    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

    2015-12-15

    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

  3. Ruthenium(II) complexes of 2-benzoylpyridine-derived thiosemicarbazones with cytotoxic activity against human tumor cell lines

    Graminha, Angelica E.; Rodrigues, Cláudia; Batista, Alzir A.; Teixeira, Letícia R.; Fagundes, Elaine S.; Beraldo, Heloisa

    2008-04-01

    Reaction of [RuCl 3(dppb)H 2O] (dppb = 1,4 bis(diphenylphospine)butane) with 2-benzoylpyridine thiosemicarbazone (H2Bz4DH) and its N(4)-methyl (H2Bz4M) and N(4)-phehyl (H2Bz4Ph) derivatives gave [RuCl(dppb)(H2Bz4DH)]Cl ( 1), [RuCl(dppb)(H2Bz4M)]Cl ( 2) and [RuCl(dppb)(H2Bz4Ph)]Cl ( 3). The cytotoxic activity of the studied compounds was tested against the MCF-7, TK-10 and UACC-62 human tumor cell lines. The precursor [RuCl 3(dppb)H 2O] exhibits cytocidal activity against the tree cell lines. H2BzDH, H2Bz4M, and [RuCl(dppb)(H2Bz4M)]Cl ( 2) show a selective cytocidal effect against the UACC-62 cell line which makes them the most promising compounds.

  4. Quinoline-2-carboxaldehyde thiosemicarbazones and their Cu(II) and Ni(II) complexes as topoisomerase IIa inhibitors.

    Bisceglie, Franco; Musiari, Anastasia; Pinelli, Silvana; Alinovi, Rossella; Menozzi, Ilaria; Polverini, Eugenia; Tarasconi, Pieralberto; Tavone, Matteo; Pelosi, Giorgio

    2015-11-01

    A series of quinoline-2-carboxaldehyde thiosemicarbazones and their copper(II) and nickel(II) complexes were synthesized and characterized. In all complexes the ligands are in the E configuration with respect to the imino bond and behave as terdentate. The copper(II) complexes form square planar derivatives with one molecule of terdentate ligand and chloride ion. A further non-coordinated chloride ion compensates the overall charge. Nickel(II) ions form instead octahedral complexes with two ligands for each metal ion, independently from the stoichiometric metal:ligand ratio used in the synthesis. Ligands and complexes were tested for their antiproliferative properties on histiocytic lymphoma cell line U937. Copper(II) derivatives are systematically more active than the ligands and the nickel complexes. All copper derivatives result in inhibiting topoisomerase IIa in vitro. Computational methods were used to propose a model to explain the different extent of inhibition presented by these compounds. The positive charge of the dissociated form of the copper complexes may play a key role in their action. PMID:26335598

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

    Chandra, Sulekh; Vandana

    2014-08-14

    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, (1)H 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. PMID:24747857

  6. Platinum(II and Palladium(II Complexes of Pyridine-2-Carbaldehyde Thiosemicarbazone as Alternative Antiherpes Simplex Virus Agents

    D. Kovala-Demertzi

    2007-01-01

    Full Text Available The cytotoxicity and the antivirus activity of Pd(II and Pt(II complexes with pyridine-2-carbaldehyde thiosemicarbazone (HFoTsc against HSV replication were evaluated on four HSV strains—two wt strains Victoria (HSV-1 and BJA (HSV-2 and two ACVR mutants with different tk gene mutations R-100 (TKA, HSV-1 and PU (TKN, HSV-2. The experiments were performed on continuous MDBK cells and four HSV 1 and HSV 2 strains were used, two sensitive to acyclovir and two resistant mutants. The five complexes of HFoTsc, [Pt(FoTscCl], [Pt(FoTsc(H2FoTsc]Cl2, [Pt(FoTsc2], [Pd(FoTsc(H2FoTsc]Cl2, and [Pd(FoTsc2], were found to be effective inhibitors of HSV replication. The most promising, active, and selective anti-HSV agent was found to be complex [Pt(FoTsc(H2FoTsc]Cl2. This complex could be useful in the treatment of HSV infections, since it is resistant to ACV mutants. PCR study of immediate early 300 bp ReIV Us1 region reveals that the complex [Pt(FoTsc(H2FoTsc]Cl2 specifically suppressed wt HSV-1 genome 2 hours after the infection, not inducing apoptosis/necrosis on the 8 hours after virus infection. The target was found to be most probably the viral, instead of the host cell DNA.

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

    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.

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

    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.

  9. Synthesis, thermal and antitumour studies of Th(IV complexes with furan-2-carboxaldehyde4-phenyl-3-thiosemicarbazone

    VINO T. CHERIYAN

    2010-06-01

    Full Text Available Thorium(IV complexes with the Schiff base furan-2-carboxaldehyde4-phenyl-3-thiosemicarbazone (L were synthesised and characterized. The composition and structure of the metal complexes were proposed based on elemental analysis, molar conductivity measurements, FTIR and 1H-NMR spectroscopy. The Schiff base behaves as a neutral bidentate ligand coordinating through the azomethine N and the thioketo S atoms. From various studies, complexes were ascertained the general formula [ThL2X4] and [ThL2Y2], where X represents NO3–, NCS–, CH3COO–, CH3CHOHCOO–, ClO4– and Y SO42–and C2O42–. The thermal behaviour of the nitrato and oxalato complexes was studied and kinetic and thermodynamic parameters were calculated using the Coats-Redfern Equation. The ligand and a representative complex [ThL2(NO34] were screened in vitro for their antitumour activity against the human cervical cancer cell line (HeLa.

  10. New potentiometric transducer based on a Mn(II) [2-formylquinoline thiosemicarbazone] complex for static and hydrodynamic assessment of azides.

    Kamel, Ayman H

    2015-11-01

    A new potentiometric transducer for selective recognition of azide is characterized and developed. The PVC plasticized based sensor incorporates Mn(II) [2-formylquinoline thiosemicarbazone] complex in the presence of tri dodecyl methyl ammonium chloride (TDMAC) as a lipophilic cationic additive. The sensor displayed a near-Nernstian response for azide over 1.0×10(-2)-1.0×10(-5) mol L(-1), with an anionic slope of -55.8±0.6 mV decade(-1) and lower limit of detection 0.34 µg mL(-1). The sensor was pH independent in the range 5.5-9 and presented good selectivity features towards several inorganic anions, and it is easily used in a flow injection system and compared with a tubular detector. The intrinsic characteristics of the detector in a low dispersion manifold were determined and compared with data obtained under a hydrodynamic mode of operation. This simple and inexpensive automation, with a good potentiometric detector, enabled the analysis of ~33 samples h(-1) without requiring pre-treatment procedures. The proposed method is also applied to the analysis of trace levels of azide in primer mixtures. Significantly improved accuracy, precision, response time, stability and selectivity were offered by these simple and cost-effective potentiometric sensor compared with other standard techniques. The method has the requisite accuracy, sensitivity and precision to determine azide ions. PMID:26452931

  11. Diorganotin Complexes of a Thiosemicarbazone, Synthesis: Properties, X-Ray Crystal Structure, and Antiproliferative Activity of Diorganotin Complexes

    Joanna Wiecek

    2010-01-01

    Full Text Available The synthesis and spectral characterization of novel diorganotin complexes with 3-hydroxypyridine-2-carbaldehyde thiosemicarbazone, HL(1, [SnMe2(L] (2, [SnBu2(L] (3, and [SnPh2(L] (4 are reported. The single-crystal X-ray structure of complex [SnPh2(L(DMSO] (5 shows that the ligand is doubly deprotonated and is coordinated as tridentate ligand. The six coordination number is completed by two carbon atoms of phenyl groups. There are two similar monomers 5a (Sn1 and 5b (Sn51 in the asymmetric unit. The monomers 5a and 5b are linked through intermolecular hydrogen bonds of N–H–O and C–H–S type. C-H→, intermolecular interactions, intra- and intermolecular hydrogen bonds stabilize this structure and leads to aggregation and a supramolecular assembly. The IR and NMR (1H, 13C and 119Sn spectroscopic data of the complexes are reported. The in vitro cytotoxic activity has been evaluated against the cells of three human cancer cell lines: MCF-7 (human breast cancer cell line, T-24 (bladder cancer cell line, A-549 (nonsmall cell lung carcinoma and a mouse L-929 (a fibroblast-like cell line cloned from strain L. Compounds 1, 3, and 4 were found active against all four cell lines. Selectivity was observed for complexes 3 and 4 which were found especially active against MCF-7 and T-24 cancer cell lines.

  12. Experimental and theoretical study of corrosion inhibition of 3-pyridinecarbozalde thiosemicarbazone for mild steel in hydrochloric acid

    Highlights: •The studied inhibitor contains both pyridine ring and Schiff base structure. •3-PCT shows excellent inhibitive properties for mild steel in HCl solution. •The results of MD simulation reveal that 3-PCT molecules adsorb on the iron surface with a nearby flat orientation. •The PZC measurement showed the mild steel surface was positively charged in HCl. -- Abstract: The corrosion inhibition effect of 3-pyridinecarboxaldehyde thiosemicarbazone (3-PCT) on mild steel was studied in 1 M HCl solution by means of weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements. The surface morphology of mild steel was examined with scanning electron microscopy (SEM) and the mechanism of inhibition was determined by the potential of zero charge (PZC) measurement at the metal–solution interface. Then molecular dynamics simulations were also executed for 3-PCT. The results show that 3-PCT is a good corrosion inhibitor, retarding both cathodic and anodic reactions in hydrochloric acid. The adsorption of 3-PCT on the mild steel surface obeys the Langmuir isotherm, and the thermodynamic parameters (Kads,Ea,ΔGads0) were also determined and discussed

  13. Growth, spectral, optical, thermal, crystallization perfection and nonlinear optical studies of novel nonlinear optical crystal—Urea thiosemicarbazone monohydrate

    Hanumantharao, Redrothu; Kalainathan, S.; Bhagavannarayana, G.

    2012-06-01

    Single crystals of organic nonlinear material urea thiosemicarbazone monohydrate (UTM) have been grown by slow evaporation method. The grown crystals were characterized by single crystal X-ray diffraction analysis reveals that sample crystallized in triclinic system with noncentrosymmetric space group P1. Powder XRD pattern confirmed that grown crystal posses highly crystalline nature. FTIR spectrum was recorded to identify the presence of functional groups and molecular structure was confirmed by 1H NMR spectrum. Material confirmation of title compound has been performed by using mass spectroscopic analysis. Elemental composition of grown crystal was confirmed by energy-dispersive spectrometry (EDS). To study the crystalline perfection of the grown crystals, high-resolution X-ray diffraction (HR-XRD) study was carried out. Thermogravimetric and differential thermal analyses were employed to understand the thermal and physio-chemical stability of the synthesized compound. UV-Vis-NIR spectrum revealed the transmission properties of the crystal specimen. Relative SHG efficiency is measured by Kurtz and Perry method and found to about 0.89 times that of standard potassium dihydrogen phosphate (KDP) crystals.

  14. Diorganotin Complexes of a Thiosemicarbazone, Synthesis: Properties, X-Ray Crystal Structure, and Antiproliferative Activity of Diorganotin Complexes

    Wiecek, Joanna; Kovala-Demertzi, Dimitra; Ciunik, Zbigniew; Zervou, Maria; Demertzis, Mavroudis A.

    2010-01-01

    The synthesis and spectral characterization of novel diorganotin complexes with 3-hydroxypyridine-2-carbaldehyde thiosemicarbazone, H2L(1), [SnMe2(L)] (2), [SnBu2(L)] (3), and [SnPh2(L)] (4) are reported. The single-crystal X-ray structure of complex [SnPh2(L)(DMSO)] (5) shows that the ligand is doubly deprotonated and is coordinated as tridentate ligand. The six coordination number is completed by two carbon atoms of phenyl groups. There are two similar monomers 5a (Sn1) and 5b (Sn51) in the asymmetric unit. The monomers 5a and 5b are linked through intermolecular hydrogen bonds of N–H–O and C–H–S type. C–H → π, intermolecular interactions, intra- and intermolecular hydrogen bonds stabilize this structure and leads to aggregation and a supramolecular assembly. The IR and NMR (1H, 13C and 119Sn) spectroscopic data of the complexes are reported. The in vitro cytotoxic activity has been evaluated against the cells of three human cancer cell lines: MCF-7 (human breast cancer cell line), T-24 (bladder cancer cell line), A-549 (nonsmall cell lung carcinoma) and a mouse L-929 (a fibroblast-like cell line cloned from strain L). Compounds 1, 3, and 4 were found active against all four cell lines. Selectivity was observed for complexes 3 and 4 which were found especially active against MCF-7 and T-24 cancer cell lines. PMID:20689713

  15. Synthesis, structural characterization and biological activities of organotin(IV) complexes with 5-allyl-2-hydroxy-3-methoxybenzaldehyde-4-thiosemicarbazone

    Rosenani A Haque; M A Salam

    2015-09-01

    The organotin(IV) complexes [MeSnCl(L)] (2), [BuSnCl(L)] (3), [PhSnCl(L)] (4) and [Me2Sn(L)] (5) were synthesized by reacting organotin(IV) chloride(s) with 5-allyl-2-hydroxy-3-methoxybenzaldehyde- 4-thiosemicarbazone [H2L], (1)] in presence of KOH in 1:2:1 molar ratio (metal salt: base:ligand). All the complexes have been characterized by elemental analyses, UV-Vis, FT-IR, 1H, 13C and 119Sn NMR spectral studies. The molecular structure of complex 5 has been confirmed by single crystal X-ray diffraction analysis. The ligand, H2L coordinates to Sn(IV) in thiolate form through phenoxide-O, azomethine-N and thiolate-S atoms. The C-Sn-C angle measured from coupling constant 1 (119Sn, 13C) for dimethyltin(IV) complex 5 is 123.4°. The 2 (119Sn, 1H) coupling constant values for complex 2 and 5 are 72.4 and 76.3 Hz, respectively. Proposed geometry for five coordinated Sn(IV) atom is a strongly distorted trigonal bipyramid. Biological studies were preformed in vitro against four bacterial strains which have shown better activities and potential as antibacterial agents.

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

    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.

  17. DNA binding, DNA cleavage, antioxidant and cytotoxicity studies on ruthenium(II) complexes of benzaldehyde 4-methyl-3-thiosemicarbazones

    Sampath, Krishnan; Sathiyaraj, Subbaiyan; Jayabalakrishnan, Chinnasamy

    2013-03-01

    Four new ruthenium(II) complexes with N(4)-methyl thiosemicarbazone ligands, (E)-2-(2-chlorobenzylidene)-N-methylhydrazinecarbothioamide (HL1) and (E)-N-methyl-2-(2-nitrobenzylidene)hydrazinecarbothioamide (HL2), were prepared and fully characterized by various spectro-analytical techniques. 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 complexes bind to DNA via intercalation. The oxidative cleavage of the complexes with CT-DNA inferred that the effects of cleavage are dose dependent. Antioxidant studies of the ligands and complexes showed the significant antioxidant activity against DPPH radical. In addition, the in vitro cytotoxicity of the ligands and complexes against MCF-7 cell line was assayed which showed higher cytotoxic activity with the lower IC50 values indicating their efficiency in killing the cancer cells even at low concentrations.

  18. Ruthenium(II) complexes containing 2-pyridineformamide- and 2-benzoylpyridine-derived thiosemicarbazones and PPh 3: NMR and electrochemical studies of cis- trans-isomerization

    Graminha, Angelica E.; Batista, Alzir A.; Mendes, Isolda C.; Teixeira, Letícia R.; Beraldo, Heloisa

    2008-04-01

    [RuCl(L)(PPh 3) 2] complexes with 2-benzoylpyridine- and 2-pyridineformamide-derived thiosemicarbazones (HL) were obtained and fully characterized. The complexes form cis- trans isomers. The cis isomer is disfavored by the sterical effect of two bulky groups close to each other whereas the trans isomer is disfavored by the electronic effect of competition of two phosphorous for π-bonding d orbitals of the metal. Our results suggest that, although both factors may be operating simultaneously, in CH 2Cl 2 solution the balance of these counterpoising effects favors the formation of the trans isomer.

  19. SPECTROSCOPIC AND BIOLOGICAL STUDIES ON NEWLY SYNTHESIZED COPPER (II AND NICKEL (II COMPLEXES WITH p -DIMETHYLAMINOBANZALDEHYDE SEMICARBAZONE AND p -DIMETHYLAMINOBANZALDEHYDE THIOSEMICARBAZONE

    Sulekh Chandra

    2012-08-01

    Full Text Available Cu (II and Ni (II complexes of general composition [ML2]X2(M = Cu(II, Ni(II; X = Cl-, NO3- weresynthesized by the condensation of metal salts with semicarbazone / thiosemicarbazone derived from p-dimethylaminobanzaldehyde. The metal complexes were characterized by elemental analysis, molar conductance, magneticsusceptibility measurements, IR and atomic absorption spectral studies. On the basis of electronic and infrared spectralstudies, the metal complexes were found to have tetrahedral geometry. The Schiff bases and their metal complexeswere tested for their antibacterial and antioxidant activities

  20. Spectroscopic and Biological Studies on Newly Synthesized Cobalt (II and Nickel (II Complexes with 2-Acetyl Coumarone Semicarbazone and 2-Acetyl Coumarone Thiosemicarbazone

    Sanjay Goel

    2013-01-01

    Full Text Available Co(II and Ni(II complexes of general composition ML2X2 (M = Co(II, Ni(II; X = Cl−, NO3 − were synthesized by the condensation of metal salts with semicarbazone/thiosemicarbazone derived from 2-acetyl coumarone. The ligands and metal complexes were characterized by NMR, elemental analysis, molar conductance, magnetic susceptibility measurements, IR, and atomic absorption spectral studies. On the basis of electronic, molar conductance and infrared spectral studies, the complexes were found to have square planar geometry. The Schiff bases and their metal complexes were tested for their antibacterial and antioxidant activities.

  1. New Application of 2-(4-N-Phenyl-3-thiosemicarbazone)-8-hydroxyquinoline as a Sensor for Relay Recognition of Cu2+ and Sulfide in Aqueous Solution

    Fluorescent and colorimetric recognition properties of 2-(4-N-phenyl-3-thiosemicarbazone)-8-hydroxyquinoline (1) in buffered aqueous solution (1% DMSO, HEPES 20 mM, pH = 7.4) have been examined. Sensor 1 displays highly selective and sensitive recognition to Cu2+ with fluorescence 'ON-OFF' performance. The in situ formed 1-Cu2+ complex exhibits an excellent selectivity toward sulfide ions with fluorescence 'OFF-ON' behavior via Cu2+ displacement approach. Thus, relay recognition of Cu2+ and sulfide by a known molecule 1 has been achieved

  2. Synthesis and theoretical study of 5-methoxyisatin-3-(N-cyclohexyl)thiosemicarbazone and its Ni(II) and Zn(II) complexes

    Kandemirli, Fatma; Arslan, Taner; Karadayı, Nevzat; Ebenso, Eno. E.; Köksoy, Baybars

    2009-12-01

    5-Methoxyisatin-3-(N-cyclohexyl)thiosemicarbazone (H 2MICT) and its Zn(II) and Ni(II) complexes have been synthesized and characterized using IR, 1H NMR, 13C-NMR, MS, UV and elemental analysis. (H 2MICT) ligand has been characterized with X-ray diffraction method also. The possible structures and IR data of the studied molecules were calculated and compared with experimental results using B3LYP/6-31G(d,p) and B3LYP/LANL2DZ methods.

  3. Liquid-liquid extraction of zinc and cadmium with 1,2-naphthoquinone thiosemicarbazone into methyl isobutyl ketone, and their simultaneous determination by atomic-absorption spectrophotometry

    Zinc and cadmium are extracted from aqueous solution with 1,2-naphtoquinone thiosemicarbazone for simultaneous determination by atomic-absorption spectrophotometry. This compound reacts with zinc and cadmium in weakly acid medium to produce chelates which are extractable into methyl isobutyl ketone. The atomic absorption is measured at 213.9 and 228.8 nm for zinc and cadmium, respectively. The sensitivity is 0.3 ng per ml of original aqueous solution and several foreign ions are tolerated in 100-fold ratio to Zn or Cd. (Author)

  4. Iron and Cobalt Complexes of 2,6-Diacetylpyridine-bis(R-thiosemicarbazone) (R=H, phenyl) Showing Unprecedented Ligand Deviation from Planarity

    Panja, Anangamohan; Campana, Charles; Leavitt, Christopher; Van Stipdonk, Michael J.; Eichhorn, David M.

    2009-01-01

    The syntheses, characterization, and single-crystal X-ray crystal structures are reported for four complexes of iron and cobalt with the pentadentate ligands, 2,6-diacetylpyridinebis(thiosemicarbazone) (H2L1) and 2,6-diacetylpyridinebis-(phenylthiosemicarbazone) (H2L2), including a cobalt dimer displaying a deviation from planarity which is unprecedented for this class of ligands and allows the ligand to occupy five positions of a pseudo-octahedral coordination sphere. This dimer reacts with KCN to produce a mononuclear complex of relevance to the active site of cobalt nitrile hydratase. PMID:20161238

  5. Comparative analysis of the cytotoxicity of substituted [phenylglyoxal bis(4-methyl-3-thiosemicarbazone)] copper(II) chelates. 2. Parabolic correlations and their implications for selective toxicity.

    Coats, E A; Milstein, S R; Pleiss, M A; Roesener, J A

    1978-08-01

    The synthesis of an extended series of para-substituted [phenylglyoxal bis(4-methyl-3-thiosemicarbazone)] copper(II) chelates is reported. Subsequent biological evaluation and regression analysis have been performed, correlating pI50 with extrathermodynamic substituent parameters. Parabolic correlations with pi have resulted which predict optimum lipophilic character of the para substituent with respect to Ehrlich ascites cytotoxicity (pi0 = -2.13) and with respect to ascites vs. liver slice cytotoxicity (pi0 = -1.31). Results indicated clearly that the chelate most toxic to the tumor cell model may not be the most selective. PMID:691005

  6. Synthesis and characterisation of molybdenum (V) and (VI) complexes of 2,6-diformyl-p-cresol-bis[4-(X-phenyl) thiosemicarbazone

    Molybdenum (V) and (VI) complexes of novel ligand 2, 6-diformyl-p-cresol bis [4-(X-phenyl) thiosemicarbazone] (where X = -H, o-CH3, m-CH3, p-CH3, p-OCH3 and p-Cl) are synthesised and characterised on the basis of elemental analyses and magnetic, IR, UV, EPR, and NMR spectral studies. The complexes have the composition [MoO2LH] and [MoOClLH]. The Schiff bases behave as dibasic tetradentate SNON donor ligands. (author)

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

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

    2015-03-15

    Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N(4)-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ=0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g||>g⊥>2.0023 and the g values in frozen DMF are consistent with the d(x2-y2) ground state. The thermal stabilities of some of the complexes were also determined. PMID:25546494

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

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

    2015-03-01

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

  9. Targeting the Metastasis Suppressor, N-Myc Downstream Regulated Gene-1, with Novel Di-2-Pyridylketone Thiosemicarbazones: Suppression of Tumor Cell Migration and Cell-Collagen Adhesion by Inhibiting Focal Adhesion Kinase/Paxillin Signaling.

    Wangpu, Xiongzhi; Lu, Jiaoyang; Xi, Ruxing; Yue, Fei; Sahni, Sumit; Park, Kyung Chan; Menezes, Sharleen; Huang, Michael L H; Zheng, Minhua; Kovacevic, Zaklina; Richardson, Des R

    2016-05-01

    Metastasis is a complex process that is regulated by multiple signaling pathways, with the focal adhesion kinase (FAK)/paxillin pathway playing a major role in the formation of focal adhesions and cell motility. N-myc downstream regulated gene-1 (NDRG1) is a potent metastasis suppressor in many solid tumor types, including prostate and colon cancer. Considering the antimetastatic effect of NDRG1 and the crucial involvement of the FAK/paxillin pathway in cellular migration and cell-matrix adhesion, we assessed the effects of NDRG1 on this important oncogenic pathway. In the present study, NDRG1 overexpression and silencing models of HT29 colon cancer and DU145 prostate cancer cells were used to examine the activation of FAK/paxillin signaling and the formation of focal adhesions. The expression of NDRG1 resulted in a marked and significant decrease in the activating phosphorylation of FAK and paxillin, whereas silencing of NDRG1 resulted in an opposite effect. The expression of NDRG1 also inhibited the formation of focal adhesions as well as cell migration and cell-collagen adhesion. Incubation of cells with novel thiosemicarbazones, namely di-2-pyridylketone 4,4-dimethyl-3-thiosemicarbazone and di-2-pyridylketone 4-cyclohexyl-4-methyl-3-thiosemicarbazone, that upregulate NDRG1 also resulted in decreased phosphorylation of FAK and paxillin. The ability of these thiosemicarbazones to inhibit cell migration and metastasis could be mediated, at least in part, through the FAK/paxillin pathway. PMID:26895766

  10. Indole-7-carbaldehyde thiosemicarbazone as a flexidentate ligand toward ZnII, CdII, PdII and PtII ions: cytotoxic and apoptosis-inducing properties of the PtII complex.

    Ibrahim, Abeer A; Khaledi, Hamid; Hassandarvish, Pouya; Mohd Ali, Hapipah; Karimian, Hamed

    2014-03-14

    A new thiosemicarbazone (LH2) derived from indole-7-carbaldehyde was synthesized and reacted with Zn(II), Cd(II), Pd(II) and Pt(II) salts. The reactions with zinc and cadmium salts in 2 : 1 (ligand-metal) molar ratio afforded complexes of the type MX2(LH2)2, (X = Cl, Br or OAc), in which the thiosemicarbazone acts as a neutral S-monodentate ligand. In the presence of potassium hydroxide, the reaction of LH2 with ZnBr2 resulted in deprotonation of the thiosemicarbazone at the hydrazine and indole nitrogens to form Zn(L)(CH3OH). The reaction of LH2 with K2PdCl4 in the presence of triethylamine, afforded Pd(L)(LH2) which contains two thiosemicarbazone ligands: one being dianionic N,N,S-tridentate while the other one is neutral S-monodentate. When PdCl2(PPh3)2 was used as the Pd(II) ion source, Pd(L)(PPh3) was obtained. In a similar manner, the analogous platinum complex, Pt(L)(PPh3), was synthesized. The thiosemicarbazone in the latter two complexes behaves in a dianionic N,N,S-tridentate fashion. The platinum complex was found to have significant cytotoxicity toward four cancer cells lines, namely MDA-MB-231, MCF-7, HT-29, and HCT-116 but not toward the normal liver WRL-68 cell line. The apoptosis-inducing properties of the Pt complex was explored through fluorescence microscopy visualization, DNA fragmentation analysis and propidium iodide flow cytometry. PMID:24442181

  11. A dual radiolabelling approach for tracking metal complexes: investigating the speciation of copper bis(thiosemicarbazonates) in vitro and in vivo.

    Hueting, Rebekka; Kersemans, Veerle; Tredwell, Matthew; Cornelissen, Bart; Christlieb, Martin; Gee, Antony D; Passchier, Jan; Smart, Sean C; Gouverneur, Véronique; Muschel, Ruth J; Dilworth, Jonathan R

    2015-05-01

    Copper(II)bis(thiosemicarbazonato) complexes such as [(64)Cu]Cu-ATSM continue to be investigated for positron emission tomography (PET) imaging of tumour hypoxia. However, the currently proposed mechanisms for the mode of action of these complexes are unable to account fully for their observed biological behaviour. In order to examine the roles of the copper metal and the ligand, we designed a pair of (123)I/(64)Cu-copper bis(thiosemicarbazonates), radiolabelled at either the metal or at the ligand. In vitro cellular retention studies of the orthogonal pair demonstrate for the first time that retention under hypoxia involves dissociation of the copper bis(thiosemicarbazone) complex, consistent with the previously suggested mechanism of reductive trapping of copper. In contrast, in vivo biodistribution and dynamic PET/SPECT imaging of the orthogonally labelled complexes underline our previous findings for [(64)Cu]Cu-ATSM and [(64)Cu]Cu-acetate, providing further support for the important contribution of copper metabolism in the in vivo hypoxia selectivity of Cu-ATSM. This dual radiolabelling approach may find applications for determining the speciation of other metal complexes in vitro and in vivo. PMID:25768310

  12. Synthesis, characterization, and in vitro anti-neoplastic activity of novel vic-dioximes bearing thiosemicarbazone side groups and their mononuclear complexes.

    Babahan, İlknur; Özmen, Ali; Orhan, Nil; Kazar, Didem; Değirmenci, Esin Hafize

    2014-04-01

    Two novel vicinal dioxime ligands containing thiosemicarbazone units, (2E)-2-[4-(diethylamino)benzylidene]-N-[(1Z,2E)-N-hydroxy-2-(hydroxyimino)ethanimidoyl]hydrazine carbothioamide (L(1)H2) and (2E)-2-[4-(dimethylamino)benzylidene]-N-[(1Z,2E)-N-hydroxy-2-(hydroxyimino)ethanimidoyl]hydrazinecarbothioamide (L(2)H2), were synthesized. Using the HL-60 human leukemia cell line, the in vitro anti-neoplastic activity of these thiosemicarbazone-oxime derivatives was evaluated. Mononuclear nickel(II), copper(II), and cobalt(II) complexes with a metal:ligand ratio of 1:2 for both the L(1)H2 and L(2)H2 ligands were also synthesized. To characterize these compounds, Fourier transform-infrared spectroscopy (FT-IR), mass spectrometry (MS), magnetic susceptibility measurements, (1)H and (13)C nuclear magnetic resonance (NMR), ultraviolet-visible (UV-Vis) absorption spectroscopy, heteronuclear multiple-bond correlation (HMQC), and elemental analysis were performed. For L(1)H2, L(2)H2, and each of their derivatives, antiproliferative effects against HL-60 cells were exhibited and the associated IpC50 values ranged from 5μM to 20μM. Furthermore, L(1)H2 and its derivatives inhibited the proliferation of HL-60 cells more effectively than L(2)H2, and 5μM [Cu(L(1)H)2] exhibited the strongest antiproliferative activity. PMID:24651042

  13. Synthesis, spectral characterization and biological evaluation of copper(II) and nickel(II) complexes with thiosemicarbazones derived from a bidentate Schiff base

    Chandra, Sulekh; Bargujar, Savita; Nirwal, Rita; Yadav, Neesha

    2013-04-01

    Complexes of copper(II) and nickel(II) of general composition M(L)2X2, have been synthesized with the ligand 1-Tetralone thiosemicarbazone (where L = 1-Tetralone thiosemicarbazone and X=Cl,1/2SO42-). The molar conductance of the complexes in fresh solution of DMSO lies in the range of 10-20 Ω-1 cm2 mol-1 indicating their non-electrolytic behavior. Thus, the complexes may be formulated as [M(L2)X2]. Ligand was characterized by mass, NMR, IR and single crystallographic studies. All the complexes were characterized by elemental analyses, magnetic moments, IR, electronic and EPR spectral studies. The IR spectral data of ligand indicated the involvement of sulfur and azomethine nitrogen in coordination to the central metal ion. The copper(II) and nickel(II) complexes were found to have magnetic moments1.93-1.96 BM and 2.91-2.94 BM corresponding to one and two unpaired electrons respectively. On the basis of molar conductance, EPR, electronic and infrared spectral studies, a tetragonal geometry has been assigned for Cu(II) chloride complex and trigonal bipyramidal to Cu(II) sulfate complex but an octahedral geometry for Ni(II) complexes. Newly synthesized ligand and its Cu(II) and Ni(II) complexes have also been screened against different bacterial and fungal species.

  14. Cinnamaldehyde and cuminaldehyde thiosemicarbazones and their copper(II) and nickel(II) complexes: a study to understand their biological activity.

    Bisceglie, Franco; Pinelli, Silvana; Alinovi, Rossella; Goldoni, Matteo; Mutti, Antonio; Camerini, Alessandro; Piola, Lorenzo; Tarasconi, Pieralberto; Pelosi, Giorgio

    2014-11-01

    This paper reports the synthesis and characterization of trans-cinnamaldehyde thiosemicarbazone (Htcin), cuminaldehyde thiosemicarbazone (Htcum) and their copper and nickel complexes. All the compounds, which on healthy cells (human fibroblasts) show a neglectable cytotoxicity, were screened in vitro in cell line U937 for their antileukemic activity. These compounds, in spite of their molecular similarity, present variegated behaviors. Htcin shows no inhibition activity in U935 cells, while both its metal complexes inhibit proliferation with IC50 at μM concentrations. The other ligand, Htcum, and its metal complexes, besides inhibiting proliferation, induce apoptosis. The cell cycle analysis highlights a G2/M checkpoint stop suggesting a possible direct action on DNA or on topoisomerase IIa. From CD and UV spectroscopy experiments, the DNA results to be not the main target of all these molecules, while both copper complexes are effective topoisomerase IIa inhibitors. All of these molecules activate caspase-9 and caspase-3, while caspase-8 activity is significantly induced by both cinnamaldehyde metal complexes. Tests on PgP and intracellular metal concentrations (determined by mean of atomic absorption spectrometry) show that the compounds tend to accumulate in the cytoplasm and that the cells do not manage to pump out copper and nickel ions. PMID:25108184

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

    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. PMID:26044321

  16. Pterostilbene carboxaldehyde thiosemicarbazone, a resveratrol derivative inhibits 17β-Estradiol induced cell migration and proliferation in HUVECs.

    Nikhil, Kumar; Sharan, Shruti; Wishard, Rohan; Palla, Srinivasa Rao; Krishna Peddinti, Rama; Roy, Partha

    2016-04-01

    Angiogenesis plays important roles in tumor growth and metastasis, thus development of a novel angiogenesis inhibitor is essential for the improvement of therapeutics against cancer. Thrombospondins-1 (TSP-1) is a potent endogenous inhibitor of angiogenesis that acts through direct effects on endothelial cell migration, proliferation, survival, and activating apoptotic pathways. TSP-1 has been shown to disrupt estrogen-induced endothelial cell proliferation and migration. Here we investigated the potential of pterostilbene carboxaldehyde thiosemicarbazone (PTERC-T), a novel resveratrol (RESV) derivative, to inhibit angiogenesis induced by female sex steroids, particularly 17β-Estradiol (E2), on Human umbilical vein endothelial cells (HUVECs) and to elucidate the involvement of TSP-1 in PTERC-T action. Our results showed that PTERC-T significantly inhibited 17β-E2-stimulated proliferation of HUVECs and induced apoptosis as determined by annexin V/propidium iodide staining and cleaved caspase-3 expression. Furthermore, PTERC-T also inhibited endothelial cell migration, and invasion in chick chorioallantoic membrane (CAM) assay. In contrast, RESV failed to inhibit 17β-E2 induced HUVECs proliferation and invasion at similar dose. PTERC-T was also found to increase TSP-1 protein expression levels in a dose-dependent manner which, however, was counteracted by co-incubation with p38MAPK or JNK inhibitors, suggesting involvement of these pathways in PTERC-T action. These results suggest that the inhibitory effect of PTERC-T on 17β-E2 induced angiogenesis is associated, at least in part, with its induction of endothelial cell apoptosis and inhibition of cell migration through targeting TSP-1. Thus, PTERC-T could be considered as a potential lead compound for developing a class of new drugs targeting angiogenesis-related diseases. PMID:26850466

  17. Radiochemotherapy plus 3-aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP, NSC #663249) in Advanced-Stage Cervical and Vaginal Cancers

    Kunos, Charles A.; Radivoyevitch, Tomas; Waggoner, Steven; Debernardo, Robert; Zanotti, Kristine; Resnick, Kimberly; Fusco, Nancy; Adams, Ramon; Redline, Raymond; Faulhaber, Peter; Dowlati, Afshin

    2013-01-01

    Objective Cervical and vaginal cancers have virally-mediated or mutated defects in DNA damage repair responses, making these cancers sensible targets for ribonucleotide reductase inhibition during radiochemotherapy. Methods We conducted a phase II study evaluating 3x weekly 2-hour intravenous 3-aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP, 25 mg/m2) co-administered with 1x weekly intravenous cisplatin (40 mg/m2) and daily pelvic radiation (45 Gy) in women with stage IB2-IVB cervical (n = 22) or stage II-IV vaginal (n = 3) cancers. Brachytherapy followed (40 Gy). Toxicity was monitored by common terminology criteria for adverse events (version 3.0). The primary end point of response was assessed by 3-month posttherapy 2-[18F] fluoro-2-deoxy-D-glucose positron emission tomography (PET/CT) and clinical examination. Results 3-AP radiochemotherapy achieved clinical responses in 24 (96% [95% confidence interval: 80-99%]) of 25 patients (median follow-up 20 months, range 2-35 months). 23 (96% [95% confidence interval: 80-99%]) of 24 patients had 3-month posttherapy PET/CT scans that recorded metabolic activity in the cervix or vagina equal or less than that of the cardiac blood pool, suggesting complete metabolic responses. The most frequent 3-AP radiochemotherapy-related adverse events included fatigue, nausea, diarrhea, and reversible hematological and electrolyte abnormalities. Conclusions The addition of 3-AP to cisplatin radiochemotherapy was tolerable and produced high rates of clinical and metabolic responses in women with cervical and vaginal cancers. Future randomized phase II and III clinical trials of 3-AP radiochemotherapy are warranted. PMID:23603372

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

    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. PMID:27133079

  19. Nickel(II complex of polyhydroxybenzaldehyde N4-thiosemicarbazone exhibits anti-inflammatory activity by inhibiting NF-κB transactivation.

    Hana Bashir Shawish

    Full Text Available 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.

  20. Novel thiosemicarbazones regulate the signal transducer and activator of transcription 3 (STAT3) pathway: inhibition of constitutive and interleukin 6-induced activation by iron depletion.

    Lui, Goldie Y L; Kovacevic, Zaklina; V Menezes, Sharleen; Kalinowski, Danuta S; Merlot, Angelica M; Sahni, Sumit; Richardson, Des R

    2015-01-01

    Pharmacologic manipulation of metal pools in tumor cells is a promising strategy for cancer treatment. Here, we reveal how the iron-binding ligands desferrioxamine (DFO), di-2-pyridylketone-4,4-dimethyl-3-thiosemicarbazone (Dp44mT), and di-2-pyridylketone 4-cyclohexyl-4-methyl-3-thiosemicarbazone (DpC) inhibit constitutive and interleukin 6-induced activation of signal transducer and activator of transcription 3 (STAT3) signaling, which promotes proliferation, survival, and metastasis of cancer cells. We demonstrate that DFO, Dp44mT, and DpC significantly decrease constitutive phosphorylation of the STAT3 transcription factor at Tyr705 in the pancreatic cancer cell lines PANC-1 and MIAPaCa-2 as well as the prostate cancer cell line DU145. These compounds also significantly decrease the dimerized STAT3 levels, the binding of nuclear STAT3 to its target DNA, and the expression of downstream targets of STAT3, including cyclin D1, c-myc, and Bcl-2. Examination of upstream mediators of STAT3 in response to these ligands has revealed that Dp44mT and DpC could significantly decrease activation of the nonreceptor tyrosine kinase Src and activation of cAbl in DU145 and MIAPaCa-2 cells. In contrast to the effects of Dp44mT, DpC, or DFO on inhibiting STAT3 activation, the negative control compound di-2-pyridylketone 2-methyl-3-thiosemicarbazone, or the DFO:Fe complex, which cannot bind cellular iron, had no effect. This demonstrates the role of iron-binding in the activity observed. Immunohistochemical staining of PANC-1 tumor xenografts showed a marked decrease in STAT3 in the tumors of mice treated with Dp44mT or DpC compared with the vehicle. Collectively, these studies demonstrate suppression of STAT3 activity by iron depletion in vitro and in vivo, and reveal insights into regulation of the critical oncogenic STAT3 pathway. PMID:25561562

  1. Variable coordinating activity of sulfur in silver(I) complexes with thiophene based N¹ -substituted thiosemicarbazones: First case of thiopheneyl-thione sulfur bridging in a dinuclear complex

    REKHA SHARMA; TARLOK S LOBANA; MANVIR KAUR; NEERAJ THATHAI; GEETA HUNDAL; JERRY P JASINSKI; RAY J BUTCHER

    2016-07-01

    Thiophene-2-carbaldehyde / acetaldehyde-N¹-substituted thiosemicarbazones {R¹R²C² = N³ - N(H)- C¹(=S)N¹HR; R¹, R², R : C₄H₃S, H, Me, Httsc- NMe; C₄H₃S, H, Et, Httsc-NEt; C₄H₃S, H, Ph, Httsc-NPh; C₄H₃S, Me, Et, Hattsc-NEt} and furan-2-carbaldehyde-N-ethyl thiosemicarbazone (C₄H₃O, H, Et, Hftsc-NEt) were reacted with silver(I) halides/silver(I) acetate in presence of triphenylphosphine in organic solvents. These reactions yielded a series of dinuclear [Ag₂(μ-Br)₂ (κ-S-Httsc-NEt)2(PPh3)2]·2MeOH 1, [Ag2Cl2(κ1-SHttsc-NPh)2(μ-S,S-Httsc-NPh)2] 2, [Ag2Cl2(μ-S-Hftsc-NEt)2(κ1-S-Hftsc-NEt)2] 4, [Ag2(μ3-N3,S-ttsc-NMe)2 (Ph3P)2]·2(CH3)2CO 5, [Ag2 (μ3-N3,S-attsc-NEt)2(Ph3P)2]·0.5(CH3)2CO 6 and mononuclear [AgBr(κ1-SHttsc-NPh)(PPh3)2]· MeCN 3 complexes, all of which have been characterized using analytical techniques, IRand NMR spectroscopy, and X-ray crystallography. Thio-ligands bind in neutral form in complexes 1-4 and in anionic form in complexes 5-6. Further, the sulfur donor atoms have shown variable coordination modes incomplexes, namely, κ1-S in 1 and 3; κ1-S, μ-S in 4; κ1-S, μ-S,S (thiopheneyl-thione) in 2 and μ3- N3, S in 5 and 6. Tertiary-phosphine (PPh3) showed dual function of ligation/de-ligation towards silver(I) chloride during the synthesis of complexes 2 and 4. The bridge bonding of Httsc-NPh in 2 through thiopheneyl ring sulfur andthione sulfur is unprecedented in metal-thiosemicarbazone chemistry.

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

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

  3. The chemistry and mechanism of thermal degradation reactions of lanthanum(III) and praseodymium(III) complexes of acetylacetone-bis(thiosemicarbazones)

    The reactions of acetylacetone with 4-phenyl, 4-(2-chlorophenyl), 4-(4-nitrophenyl) and 4-(2-methylphenyl) thiosemicarbazide yields acetylacetone-bis(thiosemicarbazone) ligands (H2L). Lanthanum(III) and praseodymium(III) complexes with these ligands of the type (Ln(L)Cl(H2O)) have been prepared. The thermal behaviour of these compounds in non-isothermal conditions was investigated using TG, DTG and DSC techniques. The intermediates obtained at the end of various thermal decomposition steps were identified from elemental analyses and infrared spectral studies. The graphical method of Coats and Redfern was employed to evaluate the kinetic parameters such as apparent activation energy and order of reaction. The heats of reaction for the different decomposition steps were calculated from DSC curves. (author)

  4. Synthesis of Co9S8 and CoS nanocrystallites using Co(II) thiosemicarbazone complexes as single-source precursors

    Amol S Pawar; Shivram S Garje

    2015-12-01

    Cubic Co9S8 and hexagonal CoS nanocrystallites were prepared by pyrolysis and solvothermal decomposition methods using Co(LH)2Cl2 and CoL2 (where LH = thiosemicarbazones of furfuraldehyde, cinnamaldehyde and 4-fluoro-acetophenone) as single-source precursors. These nanocrystallites were characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM), selected area electron diffraction, UV–Vis, PL and Raman spectroscopic techniques. From TEM images, the average grain size of asprepared cobalt sulphide nanocrystallites was found to be 7–10 nm. Depending on experimental conditions, various morphologies such as spherical, pyramidal, hollow spheres, etc. are observed in the TEM images.

  5. Thermodynamics of Complex Formation (Conductometrically Between Cu (II Ion and 4-Phenyl -1- Diacetyl Monoxime –3 -Thiosemicarbazone (BMPTS in Methanol at Different Temperatures

    Esam A Gomaa

    2015-11-01

    Full Text Available The association constant ,formation constants and Gibbs free energies are calculated from the conductometric titration curves of CuCl2 with 4 - phenyl - 2 - diacetyl monoxime - 3 - thiosemicarbazone (BMPTS in methanol at different temperatures( 293.15 K , 298.15 K , 303.15 and 308.15 K. On drawing the relation between molar conductance and the ratio of metal to ligand concentrations, different lines are obtained indicating the formation of 1:2 , 1:1 and 2:1 (M:L stoichiometric complexes. The formation constants of different complexes in methanol follow the order: Kf (2:1 › Kf (1:1 > Kf (1:2 for (M: L. As the tem perature increases, the formation constants and association constants of different complexes increase. The enthalpy and entropy of formation and association of CuCl2 with (BMPTS were also estimated and their values were also discussed

  6. Microwave Synthesis and Antimicrobial Activity of some Copper (II, Cobalt (II, Nickel (II and Chromium (III Complexes with Schiff Base 2, 6-Pyridinedi carboxaldehyde-Thiosemicarbazone

    Dr.Mohammed.Fakruddin Ali Ahmed

    2014-03-01

    Full Text Available Some novel Schiff base metal complexes of Cr(III, Co(II, Ni(II andCu(II derived from 2, 6-pyridinedicarboxaldehyde-Thiosemicarbazone(PDCTC was synthesized by conventional as well as microwavemethods. This compound wascharacterized by elemental analysis, FT-IR, Mass, molar conductanceand magneticsusceptibilitymeasurements analyses. Analytical data revealed that all the complexesexhibited 1:1 (metal: ligand ratio with a coordination number of six.The IR data showed that the ligand coordinates with the metal ions in ahexa-dentate manner. The solid state electricalconductivity of the metal complexes was also measured. Solid state electricalconductivity studies reflected a semi-conducting nature of the complexes. The Schiff base and metal complexes displayed good activity againstthe Gram-positive bacteria Staphylococcus aureus, the Gram-negative bacteriaEscherichia coli and the fungi AspergillusnigerandCandida albicans. The antimicrobialresults also indicated that the metal complexes displayed betterantimicrobial activity as compared to the Schiff bases.

  7. Transition metal complexes with thiosemicarbazide-based ligands. Part 58. Synthesis, spectral and structural characterization of dioxovanadium(V complexes with salicylaldehyde thiosemicarbazone

    LJILJANA S. VOJINOVIĆ-JEŠIĆ

    2011-06-01

    Full Text Available The first two complexes of dioxovanadium(V with salicylaldehyde thiosemicarbazone (SALTSC, of the coordination formulas [VO2(SALTSC––H]∙H2O (1 and NH4[VO2(SALTSC–2H] (2, were synthesized and characterized by elemental analysis, conductometric measurements, IR and UV–Vis spectroscopy and X-ray analysis. The complexes were obtained in the reaction of an aqueous ammoniacal solution of NH4VO3 and SALTSC. The results of the characterization showed that SALTSC was coordinated in the usual ONS tridentate mode as monoanion in complex 1 and dianion in complex 2. In both complexes, the vanadium atom is in a deformed square-pyramidal environment and is slightly shifted towards the apical oxo-ligand (» 0.52 Å.

  8. Determination of stability constants of 2-hydroxy-1-naphthalidene-thiosemicarbazone complexes with Be2+, Y3+, Pr3+, Nd3+, Dy3+, Gd3+ and UO22+

    Potentiometric studies have been carried out on metal complexes of Be2+, Y3+, Pr3+, Nd3+, Dy3+, Gd3+ and UO22+ with 2-hydroxy-1 naphthalidene-thiosemicarbazone. The proton-ligand dissociation constants (sub(p)Ksub(1) and sub(p)Ksub(2)) of the reagent and the formation constants of its metal complexes have been determined by Bjerrum's method at 25deg +- 0.1deg and at an ionic strength 0.1 M in 75:25 percent (v/v) dioxan-water medium. The validity of Born's relation was examined by studying the plot of Z2/r vs log k values of rare earth complexes of the ligand. (author)

  9. The influence of 2,3-dihydroxybenzaldehyde thiosemicarbazone on catalytic currents in the system molybdenum(VI) - potassium chlorate in acid sulfate solutions

    The polarographic catalytic current in acid solutions of Mo(VI), 2,3-dihydroxybenzaldehyde thiosemicarbazone (TSC 2,3-DHBA) and chlorate ions has been investigated. The scheme of reactions, taking place in the solutions and on the electrode, has been proposed. The increase of the catalytic current is explained by the formation of an active intermediate complex [Mo(V) TSC 2,3-DHBA (ClO-3)]. The rate constant of this complex formation K = 2.56x106 mol-1 dm3 s-1, the activation energy Ea = 15.9 kcal x mol-1 and the reaction activation entropy ΔSa≠ = -23.5 e.u. have been calculated. (authors)

  10. QSAR study of some 5-methyl/trifluoromethoxy- 1H-indole-2,3-dione-3-thiosemicarbazone derivatives as anti-tubercular agents

    Shahlaei, M.; Fassihi, A.; Nezami, A.

    2009-01-01

    In the present study, quantitative relationships between molecular structure and anti-tubercular activity of some 5-methyl/trifluoromethoxy-1H-indole-2,3-dione-3-thiosemicarbazone derivatives were discovered. The detailed application of an efficient linear method and principal component regression (PCR) for the evaluation of quantitative structure activity relationships of the studied compounds is demonstrated. Components produced by principal component analysis were used as the input for a linear model development. Results indicate a linear relationship between the principal components obtained from molecular descriptors and the inhibitory activity of this set of molecules. The maximum variance in the activity of the molecules in PCR method was 73%. The performance of the developed model was tested by several validation methods. PMID:21589807

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

    Ludmila Chiriac

    2011-06-01

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

  12. A simple colorimetric method for determination of the specific activity of spallation-produced copper-67 using phenylglyoxal (PG) bis-(4N-methyl)thiosemicarbazone (TSC) derivatives

    Copper-67 (67Cu) is a useful radioisotope for therapeutic applications and is usually available from high-energy spallation of zinc targets. Since spallation-produced 67Cu can also contain undesirable levels of nonradioactive copper (63Cu and 65Cu), which may interfere with antibody labelling, the availability of a simple inexpensive technique to determine the specific activity of 67Cu would be useful. Bis-thiosemicarbazone (TSC) derivatives of 1,2-diketones or α-ketoaldehydes such as phenylglyoxal (PG) form orange-colored complexes with copper(II) that exhibit an absorption maximum at 480 mm. Analysis of HCl target solutions of 67Cu produced at the Brookhaven National Laboratory (one sample) and the Los Alamos Scientific Laboratory (four samples) by this method gave specific activity values which corresponded very well with values obtained by ion coupling plasma analysis (ICP). (Author)

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

    Highlights: → DEABT as corrosion inhibitor for maraging steel in phosphoric acid. → Inhibition efficiency increases with increase in inhibitor concentration. → Inhibition efficiency decreases with increase in temperature. → Adsorption obeys Langmuir adsorption isotherm. - Abstract: 4-(N,N-diethylamino)benzaldehyde thiosemicarbazone (DEABT) was studied for its corrosion inhibition property on the corrosion of aged 18 Ni 250 grade maraging steel in 0.67 M phosphoric acid at 30-50 deg. C by potentiodynamic polarization, EIS and weight loss techniques. Inhibition efficiency of DEABT was found to increase with the increase in DEABT concentration and decrease with the increase in temperature. The activation energy Ea and other thermodynamic parameters (ΔGads0, ΔHads0, ΔSads0) have been evaluated and discussed. The adsorption of DEABT on aged maraging steel surface obeys the Langmuir adsorption isotherm model and the inhibitor showed mixed type inhibition behavior.

  14. Spectral studies on Co(II), Ni(II) and Cu(II) complexes with thiosemicarbazone (L 1) and semicarbazone (L 2) derived from 2-acetyl furan

    Chandra, Sulekh; Kumar, Anil

    2007-04-01

    Co(II), Ni(II) and Cu(II) complexes are synthesized with thiosemicarbazone (L 1) and semicarbazone (L 2) 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(NO 3) 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 studies and structure of a 2-hydroxyacetophenone 3-hexamethyleneiminyl thiosemicarbazonate(-2) copper(II) complex containing 1,10-phenanthroline

    John, Rohith P.; Sreekanth, A.; Prathapachandra Kurup, Maliyeckal R.; Usman, Anwar; Ibrahim, Abdul Razak; Fun, Hoong-Kun

    2003-04-01

    The spectral studies and structure of a ternary complex of copper(II) with 2-hydroxyacetophenone 3-hexamethyliminylthiosemicarbazonate (L 2-) and 1,10-phenanthroline (phen) are reported. The thiosemicarbazone binds to the metal as a dianionic ONS-donor (L 2-) ligand, and forms a complex of the stoichiometry [CuLphen]. The copper(II) complex was characterized by IR and UV/Vis spectroscopies, as well as by solid state room-temperature magnetic susceptibility. Spin Hamiltonian and bonding parameters of the compound are calculated from the EPR spectra. Computer simulation of EPR spectrum in DMF at 77 K aided the calculation of magnetic and bonding parameters of the compound. The structure of the compound is solved by single crystal X-ray diffraction. The geometry around copper is distorted square pyramidal.

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

    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(NO 3) 2 and Ni(L) 2(NO 3) 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(NO 3) 2 and Ni(L) 2(NO 3) 2 which are of tetrahedral geometry. A tetragonal geometry may be suggested for Cu(II) complexes.

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

    Lakshmi Narayana Suvarapu

    2015-12-01

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

  18. Bis(ethanol-κObis(pyridine-3-carbaldehyde-κN thiosemicarbazonebis(thiocyanato-κNiron(II–pyridine-3-carbaldehyde thiosemicarbazone (1/2

    Shao-Mei Wang

    2009-08-01

    Full Text Available The crystal structure of the title FeII complex, [Fe(NCS2(C7H8N4S2(CH3CH2OH2]·2C7H8N4S, based on the Schiff base ligand pyridine-3-carbaldehyde thiosemicarbazone (pct, results from the cocrystallization of an FeII coordination compound together with two of the pct ligands. The complex unit is mononuclear, with the central FeII ion located on a crystallographic centre of inversion and coordinated by four N atoms from two pct ligands and two thiocyanate anions. The slightly distorted octahedral coordination is completed by two O atoms from ethanol molecules. The crystal packing is accomplished intermolecular N—H...S hydrogen bonds.

  19. Synthesis, characterization and X-ray structures of new antiproliferative and proapoptotic natural aldehyde thiosemicarbazones and their nickel(II) and copper(II) complexes.

    Belicchi Ferrari, Marisa; Bisceglie, Franco; Pelosi, Giorgio; Sassi, Monica; Tarasconi, Pieralberto; Cornia, Mara; Capacchi, Silvia; Albertini, Roberto; Pinelli, Silvana

    2002-06-01

    Synthesis and characterization of new thiosemicarbazones derived from natural aldehydes (1-9) have been investigated in order to develop a research program aimed at the development of compounds with antiviral, antibacterial, and antitumor properties. These substances contain both a chain with N and S nucleophilic centers with tuberculostatic activity, and an alkyl or terpenic moiety. In addition, a few nickel(II) and copper(II) complexes (10-18), derived also from the previously studied ligands, were synthesized and characterized by means of NMR and IR techniques. The trans-2-octenal N(1)-phenylthiosemicarbazone and its nickel complex were also characterized by X-ray diffractometry. Biological studies, performed with some of these compounds, have involved both inhibition of cell proliferation and apoptosis tests in vitro on human leukemia cell line U937 to deepen our knowledge on the way these substances interfere with biological processes in leukemic cells. PMID:12031803

  20. Novel platinum(II) and palladium(II) complexes of thiosemicarbazones derived from 5-substitutedthiophene-2-carboxaldehydes and their antiviral and cytotoxic activities.

    Karaküçük-İyidoğan, Ayşegül; Taşdemir, Demet; Oruç-Emre, Emine Elçin; Balzarini, Jan

    2011-11-01

    A series of thiosemicarbazones and their platinum(II) and palladium(II) complexes have been synthesized. The chemical structures of ligands and their complexes were characterized by UV-Vis, IR, (1)H NMR, (13)C NMR, MS spectra, elemental analysis and TGA. The antiviral and cytotoxic activities of all compounds have been tested. Results of broad antiviral evaluation showed that none of the compounds evaluated endowed with anti-DNA or -RNA virus activity at subtoxic concentrations except for the palladium complex 1b. This compound exhibited slightly selective inhibition against cytomegalovirus. The platinum complex 4a exhibited the best cytostatic activities against human cervix carcinoma. Ligands 2, 4 and 5 showed cytostatic potential. The palladium complexes were in general less cytostatic than the corresponding platinum complexes or unliganded congeners. PMID:21993152

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

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

    2014-04-01

    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. PMID:24583354

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

    C.S. Carvalho

    2010-02-01

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

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

    Basken, Nathan E.; Green, Mark A.

    2009-01-01

    Introduction The 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

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

    Vasilii GRAUR

    2015-12-01

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

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

    A few metal complexes of α-oximinoacetoacet-o/p-anisidide thiosemicarbazones (OAOATS)/(OAPATS) with Ni(II), Co(II), Zn(II), Mn(II), Hg(II), Cd(II) and UO2(II) have been prepared and characterized by elemental analyses, conductivity, differential scanning calorimetry study, thermogravimetric analyses and infrared and electronic spectral measurements in conjunction with magnetic susceptibility measurements at room temperature. They have also been tested for their antimicrobial activities. (author). 24 refs., 2 tabs

  6. New Thiosemicarbazone and Talinum triangulare Vegetal Extract Formulations with Potential Anti-corrosion Activity [Novas Formulações de Tiossemicarbazonas e Extrato Vegetal de Talinum triangulare com Potencial Atividade Anticorrosão

    Mariana A . de Albuquerque; Carla M . Goulart; Ana Paula de O . Amorim; Márcia Cristina C . de Oliveira; Aurea Echevarria

    2013-01-01

    Corrosion is a process arising out of a chemical action of the environment on a particular material, causing its deterioration. It may occur in metals, concrete, organic polymers, and others. A promising alternative to prevent corrosion is the use of organic inhibitors. The search for new agents or formulations that enable the diminishing of corrosion effects is evidently necessary; therefore, this work evaluated 3 new formulations which contained thiosemicarbazones 4-hydroxy,3-methoxybenzald...

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

    Thiosemicarbazones ligands, isatin-3-thiosemicarbazone(HIT) and N-acetylisatin-3-thiosemicarbazone (HAIT), which have tridentate ONN coordinating sites were prepared. The complexes of both ligands with Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO2(VI) ions were isolated. The ligands and their metal complexes were characterized by elemental analysis, IR, UV-Vis and mass spectra, also by conductance, magnetic moment and TG-DSC measurements. All the transition metal complexes have octahedral configurations, except Cu-complexes which have planar geometry and the UO2(VI) complexes which have coordination number 8 and may acquire the distorted dodecahedral geometry. Thermal studies explored the possibility of obtaining new complexes. Inversion from octahedral to square-planar configuration occurred upon heating the parent Ni-HIAT complex to form the corresponding pyrolytic product. The antifungal activity against the tested organisms showed that some metal complexes enhanced the activity with respect to the parent ligands. (author)

  8. Simultaneous determination of the novel thiosemicarbazone anti-cancer agent, Bp4eT, and its main phase I metabolites in plasma: application to a pilot pharmacokinetic study in rats.

    Stariat, Ján; Suprunová, Vlasta; Roh, Jaroslav; Šesták, Vít; Eisner, Tomáš; Filipský, Tomáš; Mladěnka, Přemysl; Nobilis, Milan; Šimůnek, Tomáš; Klimeš, Jiří; Kalinowski, Danuta S; Richardson, Des R; Kovaříková, Petra

    2014-05-01

    Novel thiosemicarbazone metal chelators are extensively studied anti-cancer agents with marked and selective activity against a wide variety of cancer cells, as well as human tumor xenografts in mice. This study describes the first validated LC-MS/MS method for the simultaneous quantification of 2-benzoylpyridine 4-ethyl-3-thiosemicarbazone (Bp4eT) and its main metabolites (E/Z isomers of the semicarbazone structure, M1-E and M1-Z, and the amidrazone metabolite, M2) in plasma. Separation was achieved using a C18 column with ammonium formate/acetonitrile mixture as the mobile phase. Plasma samples were treated using solid-phase extraction on 96-well plates. This method was validated over the concentration range of 0.18-2.80 μM for Bp4eT, 0.02-0.37 μM for both M1-E and M1-Z, and 0.10-1.60 μM for M2. This methodology was applied to the analysis of samples from in vivo experiments, allowing for the concentration-time profile to be simultaneously assessed for the parent drug and its metabolites. The current study addresses the lack of knowledge regarding the quantitative analysis of thiosemicarbazone anti-cancer drugs and their metabolites in plasma and provides the first pharmacokinetic data on a lead compound of this class. PMID:24254882

  9. A mononuclear organoruthenium complex of a polydentate thiosemicarbazone ligand and its utilization as a building block for the synthesis of heterodinuclear Ru-Pd and Ru-Pt complexes

    Reaction of 2, 6-diacetylpyridine thiosemic arbazone with (Ru (CO)2 (PPh3)2Cl 2) in refluxing ethanol affords a mononuclear ruthenium complex (Ru), in which the thiosemicarbazone is coordinated to ruthenium as dianionic CNS- donor, along with two triphenylphosphines and a carbonyl. Using the unutilized donor atoms in the free wing of the thiosemicarbazone in the (Ru) complex two hetero-bimetallic (Ru-Pd) and (Ru-Pt ) complexes have been synthesized via re act ion of the (Ru) complex with (Pd (PPh3)2Cl 2 ) and (Pt (PPh3)2Cl 2 ) respectively. Structures of the (Ru) and (Ru-Pt ) complexes have been determined by X- ray crystallography. Structure of the (Ru-Pd) complex has been optimized by DFT method. The free wing of the thiosemicarbazone i n the (Ru) complex is utilized in binding to the second metal center in di anionic CNS-mode in the (Ru-Pd) and (Ru-Pt ) complexes, and a triphenylphosphine has occupied the fourth coordination site on the second metal center. All the three complexes show characteristic IR and 1H NMR spectra. They also display intense absorptions in the visible and ultraviolet regions. (author)

  10. Crystal structure of cesium salt of Fe(3) thiosemicarbazonate complex at 298 and 103 K. Comparison of geometrical parameters of Fe3S2O2N2 octahedral coordination fragment in high- and low-spin complexes

    The crystal structure of a high spin cesium salt of the Fe(3), thiosemicarbazonate complex, Cs[Fe(tsa)2], (tsa-salicyl aldehyde thiosemicarbazone) at room temperature and 103 K, is determined. The parameters of the rhombic cell are: a=15, 285(3), b=13.402(4), c=9.449(8)A at 298 K and a=15.161(3), b=13.340(3), c=9.394(7)A at 103 K. The space group is Pna21, Z=4, the final values of R-factors are 0.054 (298 K, 1232 reflections) and 0.041 (103 K, 1597 reflections) taking into account the absorption of X-rays using the method of calculating corrections according to the crystal form and the anomalous scattering of Cs, Fe, S atoms. The structure is built of Cs+ cations and complex anions [Fe(tsa)2]-. The specific intermolecular interactions are absent. Fe-S and Fe-N bond lengths and the values of some inner angles of the coordination polyhedron of iron atom are taken as structural characteristics during the diagnostics of the Fe(3) ion spin state in thiosemicarbazonate complexes

  11. Novel thiosemicarbazone iron chelators induce up-regulation and phosphorylation of the metastasis suppressor N-myc down-stream regulated gene 1: a new strategy for the treatment of pancreatic cancer.

    Kovacevic, Zaklina; Chikhani, Sherin; Lovejoy, David B; Richardson, Des R

    2011-10-01

    Pancreatic cancer is an aggressive neoplasm, with a mortality rate close to 100%. The most successful agent for pancreatic cancer treatment is gemcitabine, although the overall effect in terms of patient survival remains very poor. This study was initiated to evaluate a novel class of anticancer agents against pancreatic cancer. This group of compounds belongs to the dipyridyl thiosemicarbazone class that have been shown to have potent and selective activity against a range of different neoplasms in vitro and in vivo. We demonstrate for the first time in pancreatic cancer that these agents increase the expression of the growth and metastasis suppressor N-myc downstream-regulated gene 1 and its phosphorylation at Ser330 and Thr346 that is important for its activity against this tumor. In addition, these agents increased expression of the cyclin-dependent kinase inhibitor p21(CIP1/WAF1), whereas decreasing cyclin D1 in pancreatic cancer cells. Together, these molecular alterations account, in part, for the pronounced antitumor activity observed. Indeed, these agents had significantly higher antiproliferative activity in vitro than the established treatments for pancreatic cancer, namely gemcitabine and 5-fluorouracil. Studies in vivo demonstrated that a novel thiosemicarbazone, namely di-2-pyridylketone 4-cyclohexyl-4-methyl-3-thiosemicarbazone hydrochloride, completely inhibited the growth of pancreatic cancer xenografts with no evidence of marked alterations in normal tissue histology. Together, our studies have identified molecular effectors of a novel and potent antitumor agent that could be useful for pancreatic cancer treatment. PMID:21719465

  12. Synthesis and characterization of copper-64- thiosemicarbazone complexes for radionuclide cancer therapy: biodistribution study in mice by microPET imaging

    Full text: Multiple copper-thiosemicarbazone complexes of strong anticancer activity were reported in the literature. We hypothesize that a radioactive copper -thiosemicarbazone complex prepared with a radioactive copper radionuclide, such as copper-64 or copper-67, may have enhanced therapeutic efficiency combining cytotoxicity of the copper complex itself and radiotherapeutic effects of the copper radionuclide. Furthermore, a copper-64 thiosemicarbazone complex is especially attractive for targeted radionuclide cancer therapy because tumor localization of the radioactive copper complexes may be non-invasively monitored by position emission tomography (PET) when positron emitting copper isotopes, such as copper-64, are used to prepare the copper complexes. Methods: 8- hydroxyquinoline was coupled to 2-carboxaldehydethiosemicarbazide to make 8-hydroxyquinoline-2- carboxaldehydethiosemicarbazide (HQTS) holding a unique ONNS quadridentate system. Copper complex of HQTS (CuHQTS) was prepared through directly reacting copper chloride with HQTS in enthanolic solution. Anticancer activity of the CuHQTS complex was tested on human prostate cancer, neuroblastoma, and malignant glioblastoma cells by MTT assay, cell cycle arrest analysis, and FITC-Annexin V/PI FACS analysis of apoptosis. To assess bio-distribution in vivo, the HQTS ligands were radiolabeled with copper-64 at 500C for 50 min, and intravenously injected to the mice after removal of nonconjugated copper-64 radionuclides by spin column. Subsequently, the mice were subjected to whole body imaging using a Concorde microPET R4 tomograph, at 1 and 24-hour post injection of the conjugates. Upon completion of the imaging study, the mice were euthanized and the postmortem tissues were harvested, weighted and counted for radioactivity using a gamma counter (%ID/g). The mice injected with copper-64 chlorides were used as control. Results and Discussion: The CuHQTS complexes were synthesized and characterized by IR

  13. Synthesis, characterization and molecular sensing capability of fac-[Re(CO) 3(κ 2-N,N-dpktsc)Cl] where dpktsc = di-2-pyridylketone thiosemicarbazone

    Bakir, Mohammed; Brown, Ordel

    2009-07-01

    When di-2-pyridyl ketone thiosemicarbazone (dpktsc) was allowed to react with [Re(CO) 5Cl] in toluene under reflux, fac-[Re(CO) 3(κ 2-N,N-dpktsc)Cl] was isolated in good yield. The identity of fac-[Re(CO) 3(κ 2-N,N-dpktsc)Cl] was established from the results of its elemental analysis, spectroscopic, and electrochemical properties. The infrared spectra of fac-[Re(CO) 3(κ 2-N,N-dpktsc)Cl] show the facial coordination of the carbonyl groups, and the pyridyl N,N-coordination of dpktsc. 1H NMR measurements on fac-[Re(CO) 3(κ 2-N,N-dpktsc)Cl] in d6-dmso and d6-acetone confirmed the pyridyl N,N-coordination of dpktsc, and showed strong solvent dependence as manifested by the sensitivity of thioamide and ammine protons to their surroundings. The electronic absorption spectra of fac-[Re(CO) 3(κ 2-N,N-dpktsc)Cl] in protophilic solvents (dmso and dmf) display two intra-ligand charge transfer (ILCT) transitions at 476 and 360 nm and in non-protophilic solvents a single ILCT transition at 346 nm in CH 3CN and 342 nm in CH 2Cl 2. Reversible interconversion between fac-[Re(CO) 3(κ 2-N,N-dpktsc)Cl] and its conjugate base was established in protophilic solvents using a base to shift the equilibrium to the conjugate base and an acid to shift the equilibrium or conjugate base to the neutral form. Substrates in concentrations as low as 1 × 10 -10 M can be detected and determined using protophilic solutions of fac-[Re(CO) 3(κ 2-N,N-dpktsc)Cl]. When MCl 2 (M = Zn, Cd or Hg) was allowed to interact with fac-[Re(CO) 3(κ 2-N,N-dpktsc)Cl] in protophilic solvents, the intensity of the low energy ILCT band disappeared and a shift in the high energy ILCT electronic transition was observed that hints to the coordination of MCl 2 to fac-[Re(CO) 3(κ 2-N,N-dpktsc)Cl]. Electrochemical measurements on fac-[Re(CO) 3(κ 2-N,N-dpktsc)Cl] in dmf showed sequential irreversible redox processes in accord with the electrochemical reduction or oxidation of the thiosemicarbazone moiety.

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

    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. PMID:24028863

  15. 3-Nitrobenzaldehyde thiosemicarbazone

    De-Hong Wu

    2009-01-01

    Full Text Available The molecule of the title compound, C8H8N4O2S, adopts an E configuration about both the C—N bonds. In the crystal structure, adjacent molecules are linked by intermolecular N—H...S hydrogen-bonding interactions, forming chains running parallel to the b axis.

  16. 4-Methylbenzaldehyde thiosemicarbazone

    Jian Zhang; Hao Geng; Ling-hua Zhuang; Guo-wei Wang

    2009-01-01

    The title compound, C9H11N3S, was prepared by reacting 4-methylbenzaldehyde with thiosemicarbazide. An intramolecular N—H...N hydrogen bond helps to establish the observed molecular conformation. The crystal packing is realized by intermolecular N—H...S hydrogen bonds.

  17. 4-Methylbenzaldehyde thiosemicarbazone

    Jian Zhang

    2009-09-01

    Full Text Available The title compound, C9H11N3S, was prepared by reacting 4-methylbenzaldehyde with thiosemicarbazide. An intramolecular N—H...N hydrogen bond helps to establish the observed molecular conformation. The crystal packing is realized by intermolecular N—H...S hydrogen bonds.

  18. Ferrocene-1-carbaldehyde thiosemicarbazone

    M. R. Vikneswaran

    2010-06-01

    Full Text Available The asymmetric unit of the title compound, [Fe(C5H5(C7H8N3S], consists of two crystallographically independent molecules, A and B. The cyclopentadienyl (Cp rings in both molecules adopt an eclipsed conformation and are parallel to each other, forming dihedral angles of 2.5 (3 and 1.1 (3°, respectively. The mean plane of the semicarbazone group is coplanar with the attached Cp ring in molecule A, whereas it is twisted away in molecule B. In the crystal structure, intermolecular N—H...S hydrogen bonds link the molecules into two-dimensional planes parallel to the ab plane. The structure is further consolidated by C—H...π interactions.

  19. 3-Nitrobenzaldehyde thiosemicarbazone

    De-Hong Wu; Zhu-Feng Li; You-Hong Zhang

    2009-01-01

    The molecule of the title compound, C8H8N4O2S, adopts an E configuration about both the C—N bonds. In the crystal structure, adjacent molecules are linked by intermolecular N—H...S hydrogen-bonding interactions, forming chains running parallel to the b axis.

  20. Benzaldehyde thiosemicarbazone monohydrate

    Sheng-Jiu Gu

    2008-08-01

    Full Text Available In the title compound, C8H9N3S·H2O, intramolecular N—H...N hydrogen bonding contributes to the molecular conformation. Water molecules are involved in intermolecular N—H...O and O—H...S hydrogen bonds, which link the molecules into ribbons extended along the a axis. Weak intermolecular N—H...S hydrogen bonds link these ribbons into layers parallel to the ab plane with the phenyl rings pointing up and down.