Sample records for 2-acetylpyridine n4-phenyl thiosemicarbazone

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

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    Soares, Marcella Araugio; Pesquero, Jorge Luiz [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Fisiologia e Biofisica], e-mail:; 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:


    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)

  2. 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

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    Soares, Marcella Araugio


    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{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

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

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    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


    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)

  4. 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 (United States)

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


    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.

  5. 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

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    Silva, Paulo Roberto Ornelas da


    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

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


    Despaigne,Angel A. R.; Vieira,Lorena F.; Mendes,Isolda C.; Costa,Fernanda B. da; Speziali,Nivaldo L.; Beraldo, Heloisa


    Reaction of n-butyltin trichloride, [Bu nSnCl3], and phenyltin trichloride, [PhSnCl3], with 2-acetylpyridine benzoyl hydrazone (H2AcPh), 2-acetylpyridine para-chloro-benzoyl hydrazone (H2AcpClPh) and 2-acetylpyridine para-nitro-benzoyl hydrazone (H2AcpNO2Ph) gave [Bu nSn(2AcPh)Cl2] (1), [Bu nSn(2AcpClPh)Cl2] (2), [Bu nSn(2AcpNO2Ph)Cl2] (3), [PhSn(2AcPh)Cl2] (4), [PhSn(2AcpClPh)Cl2] (5) and [PhSn(2AcpNO2Ph)Cl2] (6) as products. Among the hydrazones H2AcpClPh proved to be the most active agains...

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

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    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: [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)


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

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    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


    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)

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

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    Michael A. O'Donnell


    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.

  10. Benzaldehyde thiosemicarbazone

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    Xiu-Ping Ju


    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.

  11. Redefining the structure-activity relationships of 2,6-methano-3-benzazocines. 5. Opioid receptor binding properties of N-((4'-phenyl)-phenethyl) analogues of 8-CAC. (United States)

    VanAlstine, Melissa A; Wentland, Mark P; Cohen, Dana J; Bidlack, Jean M


    A series of aryl-containing N-monosubstituted analogues of the lead compound 8-[N-((4'-phenyl)-phenethyl)]-carboxamidocyclazocine were synthesized and evaluated to probe a putative hydrophobic binding pocket of opioid receptors. Very high binding affinity to the mu opioid receptor was achieved though the N-(2-(4'-methoxybiphenyl-4-yl)ethyl) analogue of 8-CAC. High binding affinity to mu and very high binding affinity to kappa opioid receptors was observed for the N-(3-bromophenethyl) analogue of 8-CAC. High binding affinity to all three opioid receptors were observed for the N-(2-naphthylethyl) analogue of 8-CAC.

  12. Novel thiosemicarbazones of the ApT and DpT series and their copper complexes: identification of pronounced redox activity and characterization of their antitumor activity. (United States)

    Jansson, Patric J; Sharpe, Philip C; Bernhardt, Paul V; Richardson, Des R


    The novel chelators 2-acetylpyridine-4,4-dimethyl-3-thiosemicarbazone (HAp44mT) and di-2-pyridylketone-4,4-dimethyl-3-thiosemicarbazone (HDp44mT) have been examined to elucidate the structure-activity relationships necessary to form copper (Cu) complexes with pronounced antitumor activity. Electrochemical studies demonstrated that the Cu complexes of these ligands had lower redox potentials than their iron complexes. Moreover, the Cu complexes where the ligand/metal ratio was 1:1 rather than 2:1 had significantly higher intracellular oxidative properties and antitumor efficacy. Interestingly, the 2:1 complex was shown to dissociate to give significant amounts of the 1:1 complex that could be the major cytotoxic effector. Both types of Cu complex showed significantly more antiproliferative activity than the ligand alone. We also demonstrate the importance of the inductive effects of substituents on the carbonyl group of the parent ketone, which influence the Cu(II/I) redox potentials because of their proximity to the metal center. The structure-activity relationships described are important for the design of potent thiosemicarbazone Cu complexes.

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

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


    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.

  14. 1H, 13C, and 15N NMR Studies of Au(III and Pd(II Chloride Complexes and Organometallics with 2-Acetylpyridine and 2-Benzoylpyridine

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    Daria Niedzielska


    Full Text Available Au(III and Pd(II chloride complexes with N(1,O-chelating 2-acetylpyridine (2apy and N(1- monodentately binding 2-benzoylpyridine (2bz′py-[Pd(2apyCl2], [Au(2bz′pyCl3], trans-[Pd(2bz′py2Cl2], as well as Au(III chloride organometallics with monoanionic forms of 2apy or 2bz′py, deprotonated at the acetyl or benzyl side groups (2apy*, 2bz′py*-[Au(2apy*Cl2], [Au(2bz′py*Cl2], were studied by 1H, 13C, and 15N NMR. 1H, 13C, and 15N coordination shifts (i.e., differences between the respective , , and chemical shifts of the same atom in the complex and ligand molecules: , , were discussed in relation to the molecular structures and coordination modes, as well as to the factors potentially influencing nuclear shielding. Analogous NMR measurements were performed for the new (2bz′pyH[AuCl4] salt.

  15. Study on Complexes of 2-Acetylpyridene Thiosemicarbazone with Cu (Ⅱ) and Their Antibacterial Activities%2-乙酰吡啶缩氨基硫脲铜配合物的合成及其抑菌活性研究

    Institute of Scientific and Technical Information of China (English)



    The complexes[CuLX](X=Br,I,NCS) of 2-acetylpyridine thiosemicarbazone(HL) have been isolated and characterized by elemental analyses, molar conductance, magnetic moment and IR spectra. Antibacterial activities of ligand and complexes have been evaluated against S. aureus,B. sugtilis and E. coli.%合成了2-乙酰呲啶缩氨基硫脲与铜Cu(Ⅱ)配合物[CuLX](X=Br,I,NCS),并通过元素分析、摩尔电导、磁矩和红外光谱进行了表征.抑菌实验研究表明,配合物的活性明显高于配体本身,且[CuLI]对三种细菌完全抑制.

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

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


    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.

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

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    Perez-Rebolledo, Anayive [Universidade Federal de Minas Gerais, Departamento de Quimica (Brazil); Ardisson, Jose D., E-mail: [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: [Universidade Federal de Minas Gerais, Departamento de Quimica (Brazil)


    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.


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    Negi Parul


    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.

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

    DEFF Research Database (Denmark)

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


    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 9.9nM, 14.4nM, and 8.1nM, 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 10μM. Thiosemicarbazone analogue 8 significantly inhibited the invasive potential of PC-3ML prostate cancer cells by 92% at 5μ...

  20. Synthesis and Structure of Bis(4-nitrobenzaldehyde thiosemicarbazone) Cadmium Iodide

    Institute of Scientific and Technical Information of China (English)


    The title complex, bis(4-nitrobenzaldehyde thiosemicarbazone) cadmium iodide (C16H16CdI2N8O4S2) crystallizes in the triclinic system, space group P1 with a=9.632(2), b=11.227(2), c=14.031(3), α= 67.50(3), β= 86.99(3), γ= 66.64(3)°, V=1278.13, Z = 2, Dc = 2.117gcm-3, F(000) = 772, μ =3.472mm-1 MoKα radiation (λ=0.71073), R = 0.0443, wR= 0.1425 for 4529 observed reflections [I>2σ(I)] of 4731 independent reflections. The result shows that the structure contains CdL2I2 (where L = 4-nitrobenzaldehyde thiosemicarbazone) distorted tetrahedral units in which the two ligands are S-bonded as monodentate to cadmium ion; the two iodide ions are also coordinated to Cd(II).


    Directory of Open Access Journals (Sweden)

    Georges C. Accrombessi


    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.

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

    Directory of Open Access Journals (Sweden)

    Marina Azevedo Souza


    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.

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

    DEFF Research Database (Denmark)

    Larsen, Dennis

    is presented. This represents the first use, to the best of the author’s knowledge, of thiosemicarbazones for organocatalysis. Guided by kinetics studies, a range of catalysts were developed and evaluated, and this showed that thiosemicarbazone catalysts are highly tuneable. The best thiosemicarbazone catalyst......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...... gave a 50-fold higher second-order rate constant than the best thiourea catalyst reported for this transformation. A dual Hammett plot analysis and interaction studies by NMR spectroscopy lends support to a reaction mechanism proceeding via an asynchronous [2+2] cycloaddition. The third and final part...

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

    Directory of Open Access Journals (Sweden)

    Abdullah M. Asiri


    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.

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

    Directory of Open Access Journals (Sweden)

    Cecília M. A. de Oliveira


    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.

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

    Directory of Open Access Journals (Sweden)

    Saulo Feheiberg Pinto Braga

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

  7. Investigation of the Biological Properties of (HeteroAromatic Thiosemicarbazones

    Directory of Open Access Journals (Sweden)

    Jaroslaw Polanski


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

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

    Energy Technology Data Exchange (ETDEWEB)

    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)


    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.

  9. Intermolecular interaction of thiosemicarbazone derivatives to solvents and a potential Aedes aegypti target (United States)

    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.


    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.

  10. Synthesis of new hyodeoxycholic acid thiosemicarbazone derivatives under solvent-free conditions using microwave

    Institute of Scientific and Technical Information of China (English)

    Zhi Chuan Shi; Zhi Gang Zhao; Xing Li Liu; Yu Chen


    An efficient and simple method for synthesis of new hyodeoxycholic acid thiosemicarbazone derivatives under solvent-free conditions using microwave has been developed. Its main advantages are short reaction times, good conversions and the environmentally friendly nature of the process. The preliminary results indicate that some of these compounds possess inhibitory effects against E. coli.

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

    Institute of Scientific and Technical Information of China (English)

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


    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.

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

    Institute of Scientific and Technical Information of China (English)

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


    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.

  13. Synthesis and structure-activity relationship study of a new series of antiparasitic aryloxyl thiosemicarbazones inhibiting Trypanosoma cruzi cruzain. (United States)

    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


    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.

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

    Indian Academy of Sciences (India)

    Indrani Pal; Falguni Basuli; Samaresh Bhattacharya


    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.

  15. Conformational restriction of aryl thiosemicarbazones produces potent and selective anti-Trypanosoma cruzi compounds which induce apoptotic parasite death. (United States)

    Magalhaes Moreira, Diogo Rodrigo; de Oliveira, Ana Daura Travassos; Teixeira de Moraes Gomes, Paulo André; de Simone, Carlos Alberto; Villela, Filipe Silva; Ferreira, Rafaela Salgado; da Silva, Aline Caroline; dos Santos, Thiago André Ramos; Brelaz de Castro, Maria Carolina Accioly; Pereira, Valéria Rego Alves; Leite, Ana Cristina Lima


    Chagas disease, caused by Trypanosoma cruzi, is a life-threatening infection leading to approximately 12,000 deaths per year. T. cruzi is susceptible to thiosemicarbazones, making this class of compounds appealing for drug development. Previously, the homologation of aryl thiosemicarbazones resulted in an increase in anti-T. cruzi activity in comparison to aryl thiosemicarbazones without a spacer group. Here, we report the structural planning, synthesis and anti-T. cruzi evaluation of new aryl thiosemicarbazones (9a-x), designed as more conformationally restricted compounds. By varying substituents attached to the phenyl ring, substituents were observed to retain, enhance or greatly increase the anti-T. cruzi activity, in comparison to the nonsubstituted derivative. In most cases, hydrophobic and bulky substituents, such as bromo, biphenyl and phenoxyl groups, greatly increased antiparasitic activity. Specifically, thiosemicarbazones were identified that inhibit the epimastigote proliferation and were toxic for trypomastigotes without affecting mouse splenocytes viability. The most potent anti-T. cruzi thiosemicarbazones were evaluated against cruzain. However, inhibition of this enzyme was not observed, suggesting that the compounds work through another mechanism. In addition, examination of T. cruzi cell death showed that these thiosemicarbazones induce apoptosis. In conclusion, the structural design executed within the series of aryl thiosemicarbazones (9a-x) led to the identification of new potent anti-T. cruzi agents, such as compounds (9h) and (9r), which greatly inhibited epimastigote proliferation, and demonstrated a toxicity for trypomastigotes, but not for splenocytes. Mechanistically, these compounds do not inhibit the cruzain, but induce T. cruzi cell death by an apoptotic process.

  16. Thiosemicarbazone modification of 3-acetyl coumarin inhibits Aβ peptide aggregation and protect against Aβ-induced cytotoxicity. (United States)

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


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

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

    Directory of Open Access Journals (Sweden)

    Brian J. Anderson


    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. Synthesis, biological evaluation and molecular docking of N-phenyl thiosemicarbazones as urease inhibitors. (United States)

    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


    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.

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

    Directory of Open Access Journals (Sweden)

    Tudor Rosu


    Full Text Available The chelating behavior of the thiosemicarbazone derivatives of 2-hydroxy-8-R-tricyclo[,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.

  20. The versatility of salicylaldehyde thiosemicarbazone in the determination of copper in blood using adsorptive stripping voltammetry. (United States)

    Mahajan, Rakesh Kumar; Walia, T P S; Sumanjit; Lobana, T S


    The adsorptive cathodic stripping voltammetry technique (AdCSV) is used to determine copper(II) using salicylaldehyde thiosemicarbazone (N, S- donor) as a complexing agent on hanging mercury drop electrode at pH 9.3. Variable factors affecting the response, i.e. the concentration of ligand, pH, adsorption potential and adsorption time are assessed and optimized. The adsorbed complex of copper(II) and salicylaldehyde thiosemicarbazone gives a well defined cathodic stripping peak current at -0.35 V, which has been used for the determination of copper in the concentration range of 7.85 x 10(-9) to 8.00 x 10(-6)M with accumulation time of 360 s at -0.1 V versus Ag/AgCl. This technique has been applied for the determination of copper in various digested samples of whole blood at trace levels.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

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

    Indian Academy of Sciences (India)

    Tarlok S Lobana


    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.

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

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


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

  4. In vitro antiparasitic activity of new thiosemicarbazones in strains of Trypanosoma cruzi. (United States)

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


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

  5. Complexes of 2-acetyl-gamma-butyrolactone and 2-furancarbaldehyde thiosemicarbazones: antibacterial and antifungal activity. (United States)

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


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

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

    Institute of Scientific and Technical Information of China (English)

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


    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.

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

    Indian Academy of Sciences (India)

    Piyali Paul; Samaresh Bhattacharya


    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.

  8. Microwave synthesis of mixed ligand diimine-thiosemicarbazone complexes of ruthenium(II): biophysical reactivity and cytotoxicity. (United States)

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


    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)(2)Ru(thiosemicarbazone)](PF(6))(2) and [(phen)(2)Ru(thiosemicarbazone)](PF(6))(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.

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

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


    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

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


    Agarwal, Ram K. [رام اجراول; Prasad, Surendra; GAHLOT, Neetu


    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...

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

    Directory of Open Access Journals (Sweden)

    Marc-Andre LeBlanc


    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.

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

    Institute of Scientific and Technical Information of China (English)

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


    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.

  13. 1-Pyrenecarboxaldehyde thiosemicarbazone:A novel fluorescent molecular sensor towards mercury(Ⅱ)ion

    Institute of Scientific and Technical Information of China (English)

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


    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.

  14. Electron Microscopy of Intracellular Protozoa. (United States)


    described by Casero et al.(1). For electron microscopy, 50 x 106 organisms in 5 ml of incubation medium (1) were treated with 10 0 DMSO(control cultures... Casero , R.A., Klayman, D.L., Childs, G.E., Scoville, J.P., and Desjardins, R.E. 1980. Activity of 2-acetylpyridine thiosemicarbazones against

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

    Institute of Scientific and Technical Information of China (English)

    Qing Han Li; Zhi Gang Zhao


    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.

  16. Lanthanum(III) and praseodymium(III) complexes with isatin thiosemicarbazones (United States)

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


    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.

  17. Cytotoxic gallium complexes containing thiosemicarbazones derived from 9-anthraldehyde: Molecular docking with biomolecules (United States)

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


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

  18. 2-Hydroxy-4-n-butoxy-5-bromoacetophenone thiosemicarbazone as an extractive spectrophotometric reagent for nickel

    Directory of Open Access Journals (Sweden)

    K. N. Patel


    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.

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

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


    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).

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

    Directory of Open Access Journals (Sweden)

    Quintell Tillison


    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

  1. Novel aldehyde and thiosemicarbazone derivatives: Synthesis, spectroscopic characterization, structural studies and molecular docking studies (United States)

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


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

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

    Institute of Scientific and Technical Information of China (English)

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


    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.

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

    Indian Academy of Sciences (India)

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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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: [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)


    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.

  5. Copper and conquer: copper complexes of di-2-pyridylketone thiosemicarbazones as novel anti-cancer therapeutics. (United States)

    Park, Kyung Chan; Fouani, Leyla; Jansson, Patric J; Wooi, Danson; Sahni, Sumit; Lane, Darius J R; Palanimuthu, Duraippandi; Lok, Hiu Chuen; Kovačević, Zaklina; Huang, Michael L H; Kalinowski, Danuta S; Richardson, Des R


    Copper is an essential trace metal required by organisms to perform a number of important biological processes. Copper readily cycles between its reduced Cu(i) and oxidised Cu(ii) states, which makes it redox active in biological systems. This redox-cycling propensity is vital for copper to act as a catalytic co-factor in enzymes. While copper is essential for normal physiology, enhanced copper levels in tumours leads to cancer progression. In particular, the stimulatory effect of copper on angiogenesis has been established in the last several decades. Additionally, it has been demonstrated that copper affects tumour growth and promotes metastasis. Based on the effects of copper on cancer progression, chelators that bind copper have been developed as anti-cancer agents. In fact, a novel class of thiosemicarbazone compounds, namely the di-2-pyridylketone thiosemicarbazones that bind copper, have shown great promise in terms of their anti-cancer activity. These agents have a unique mechanism of action, in which they form redox-active complexes with copper in the lysosomes of cancer cells. Furthermore, these agents are able to overcome P-glycoprotein (P-gp) mediated multi-drug resistance (MDR) and act as potent anti-oncogenic agents through their ability to up-regulate the metastasis suppressor protein, N-myc downstream regulated gene-1 (NDRG1). This review provides an overview of the metabolism and regulation of copper in normal physiology, followed by a discussion of the dysregulation of copper homeostasis in cancer and the effects of copper on cancer progression. Finally, recent advances in our understanding of the mechanisms of action of anti-cancer agents targeting copper are discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Tenorio, Romulo P.; Goes, Alexandre J.S. [Universidade Federal de Pernambuco, Recife, PE (Brazil). Dept. de Antibioticos]. E-mail:; 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


    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)

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

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


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

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

    Directory of Open Access Journals (Sweden)

    Atef Arfan


    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].

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

    Directory of Open Access Journals (Sweden)

    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.

  12. Synthesis and Evaluation of New Benzodioxole- Based Thiosemicarbazone Derivatives as Potential Antitumor Agents

    Directory of Open Access Journals (Sweden)

    Mehlika Dilek Altıntop


    Full Text Available New benzodioxole-based thiosemicarbazone derivatives were synthesized and evaluated for their cytotoxic effects on A549 human lung adenocarcinoma, C6 rat glioma and NIH/3T3 mouse embryonic fibroblast cells. In order to examine the correlation between anticancer activity and cholinesterases, the compounds were evaluated for their inhibitory effects on AChE and BuChE. The most effective anticancer agents were investigated for their effects on DNA synthesis, apoptosis and mitochondrial membrane potential. 4-(1,3-Benzodioxol-5-yl-1-([1,1′-biphenyl]-4-ylmethylenethiosemicarbazide (5 was identified as the most promising anticancer agent against C6 and A549 cell lines due to its inhibitory effects on C6 and A549 cells and low toxicity to NIH/3T3 cells. Compound 5 increased early and late apoptosis in A549 and C6 cells. Compound 5 also caused disturbance on mitochondrial membrane potential and showed DNA synthesis inhibitory activity in A549 and C6 cells. Compound 5 was investigated for SIRT1 inhibitory activity to provide mechanistic insight and for that purpose docking studies were also performed for this compound on SIRT1. On the other hand, compound 5 did not show any inhibitory activity against AChE and BuChE. This outcome pointed out that there is no relationship between anticancer activity of compound 5 and cholinesterases.

  13. Cyclopentanone thiosemicarbazone, a new complexing agent for copper determination in biological samples by adsorptive stripping voltammetry. (United States)

    Mahajan, Rakesh Kumar; Walia, T P S; Sumanjit; Lobana, T S


    A selective and sensitive stripping voltammetric method for the determination of trace amounts of copper(II) with cyclopentanone thiosemicarbazone (CPTSC) is presented. The method is based on the adsorptive accumulation of the resulting copper-CPTSC complex on a hanging mercury drop electrode, followed by the stripping voltammetric measurements at the reduction current of the adsorbed complex at -0.37 V vs. Ag/AgCl. The optimal conditions for the stripping analysis of copper include pH 9.3, deposition time of 120 s, and a deposition potential of -0.1 V (vs. Ag/AgCl). The peak current is linearly proportional to the copper concentration over a range 3.14 x 10(-9) M to 1.57 x 10(-6) M with a limit of detection of 1.57 x 10(-9) M. The technique has been applied to the determination of copper in biological samples, like urine and whole blood.

  14. Intracellular reduction/activation of a disulfide switch in thiosemicarbazone iron chelators (United States)

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


    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. Identification of semicarbazones, thiosemicarbazones and triazine nitriles as inhibitors of Leishmania mexicana cysteine protease CPB. (United States)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    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.

  17. Structure and Luminescence Property of a Hexanuclear Silver(I) Cluster Containing Pyridine-3-carboxaldehyde Thiosemicarbazone

    Institute of Scientific and Technical Information of China (English)

    SUN Qiao-Zhen; CHAI Li-Yuan


    A new hexanuclear silver(I) compound containing thiosemicarbazone with group of 3-pyridine was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spectrum.The title compound 3 crystallizes in monoclinic,space group C2/m with a = 18.6523(9),b = 24.7519(11),c = 22.4542(15) ,β = 93.4960(10)°,V = 10347.4(10)3,C68H104Ag6N30O8S6,Mr = 2309.39,Dc = 1.482g/cm3,μ(MoKα) = 1.293 mm-1,F(000) = 4656,Z = 4,the final R = 0.0544 and wR = 0.1580 for 6733 observed reflections(I 〉 2σ(I)).In the structure,two Ag6L36(L3 = pyridine-3-carboxaldehyde thiosemicarbazone) clusters are contained.In each cluster,the S atom of ligand L3 served as a triply bridged chelator to connect the six silver atoms into a Ag6L36 cluster.Luminescence investigation revealed that the band at 630 nm was attributed to cluster-centered(CC) electron transfer,and those at 493 and 530 nm to the LMCT and CC transitions,respectively.

  18. Synthesis, Structure and Comparison of Luminescent Property between Two Hexanuclear Silver(I) Thiosemicarbazone Clusters

    Institute of Scientific and Technical Information of China (English)

    SUN Qiao-Zhen; LIAO Song-Yi; CHAI Li-Yuan; XU Xiao-Wen3; YAO Jun-Jun; FANG Qiong-Jia-Li


    A new silver(Ⅰ) compound 4 containing thiosemicarbazone with group 2-quinoline was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. Compound 4 crystallizes in triclinic, space group P1 with a = 12.2710(9), b = 16.9281(13), c = 17.2984(13), α = 112.8500(10), β = 103.4890(10), γ = 102.6860(10)°, V = 3020.9(4) 3, C80H94Ag6N28O6S6, Mr = 2383.41, Dc = 1.310 g/cm3, μ(MoKα) = 1.108 mm-1, F(000) = 1196, Z = 1, the final R = 0.0567 and wR = 0.1368 for 5112 observed reflections (I 〉 2σ(I)). Similar to the structure of compound 2 we have reported, compound 4 also exhibits a hexanuclear silver(Ⅰ) cluster. In the cluster, the S atom of ligand L4 (L4 = 2-quinolinecarboxaldehyde thiosemicarbazone) serves as a triply bridged chelator to connect the six silver atoms into a Ag6L46 cluster. The luminescence property of 4 is investigated at room temperature and compared with that of 2.

  19. Structure and Luminescence Property of a Hexanuclear Silver(Ⅰ) Cluster Containing Benzaldehyde Thiosemicarbazone

    Institute of Scientific and Technical Information of China (English)

    SUN Qiao-Zhen


    A new hexanuclear silver (I) compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in triclinic, space group P with a = 11.611(3), b = 15.610(5), c = 15.624(7) , α = 113.942(6), β = 104.520(6), γ = 104.230(4)°, V = 2304.1(14) 3, C60H77Ag6N22O4.5S6, Mr = 2018.02, Dc = 1.454 g/cm3, μ(MoKα) = 1.435 mm-1, F(000) = 1005, Z = 1, the final R = 0.0468 and wR = 0.1474 for 6608 observed reflections (I 2σ(I)). In the structure, the S atom of the ligand L2 (L2 = benzaldehyde thiosemicarbazone) served as a triply bridged chelator to connect the six silver atoms into a Ag6L26 cluster. The luminescence property of compound 2 was investigated at room temperature.

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

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


    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.

  1. Targeting triple negative breast cancer cells by N3-substituted 9,10-Phenanthrenequinone thiosemicarbazones and their metal complexes (United States)

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


    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.

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

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


    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.

  3. In vitro cytotoxic, antibacterial, antifungal and urease inhibitory activities of some N4- substituted isatin-3-thiosemicarbazones. (United States)

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


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

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

    Indian Academy of Sciences (India)

    Rupesh Narayana Prabhu; Samudranil Pal


    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.

  5. Vibrational, NMR and UV-visible spectroscopic investigation and NLO studies on benzaldehyde thiosemicarbazone using computational calculations (United States)

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


    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.

  6. New Copper(Ⅱ) and Nickel(Ⅱ) Complexes of 4-Morpholinoacetophenone Thiosemicarbazone: Structural, Electrochemical and Antimicrobial Studies

    Institute of Scientific and Technical Information of China (English)

    BINGOL Haluk; COSKUN Ahmet; AKGEMCI Emine Guler; KAYA Basturk; ATALAY Tevfik


    4-Morpholinoacetophenone thiosemicarbazone, MAPT, and its nickel(Ⅱ) and copper(Ⅱ) complexes have been prepared and characterized by elemental analysis, magnetic susceptibility, spectral methods (FT-IR, 1H NMR) and cyclic voltammetry. Electrochemical behaviors of the complexes have been studied by cyclic voltammetry in DMF media showing metal centered reduction processes for both of them. The redox properties, nature of the electrode processes and the stability of the complexes were discussed. [Cu(MAPT)2]Cl2 complex shows Cu(Ⅱ)/Cu(I) couple and quasi-reversible wave associated with the Cu(Ⅲ)/Cu(Ⅱ) process. The reduction/oxidation potential values depend on the structures of complexes. Also, the antimicrobial activities of these complexes were determined against S. aureus, E. coli and B. subtilis.

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

    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


    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.

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

    Directory of Open Access Journals (Sweden)



    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.

  9. Eco-Friendly Synthesis of Some Thiosemicarbazones and Their Applications as Intermediates for 5-Arylazothiazole Disperse Dyes. (United States)

    Gaffer, Hatem E; Khalifa, Mohamed E


    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.

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

    Directory of Open Access Journals (Sweden)

    Hatem E. Gaffer


    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. Synthèse, Caractérisation et Application dans l’Environnement d’un Nouveau Ligand, dérivé de la Thiosemicarbazone.




    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 ...

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

    Energy Technology Data Exchange (ETDEWEB)

    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:


    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.

  13. Synthesis, X-ray structure and in vitro cytotoxicity studies of Cu(I/II) complexes of thiosemicarbazone: special emphasis on their interactions with DNA. (United States)

    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


    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.

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

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


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

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

    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


    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.

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

    Directory of Open Access Journals (Sweden)

    Arumugam Manimaran


    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.

  17. Synthesis, thermal and antitumour studies of Th(IV complexes with furan-2-carboxaldehyde4-phenyl-3-thiosemicarbazone

    Directory of Open Access Journals (Sweden)



    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.

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

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


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

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

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


    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.

  20. Synthesis, structural characterization and biological activities of organotin(IV) complexes with 5-allyl-2-hydroxy-3-methoxybenzaldehyde-4-thiosemicarbazone

    Indian Academy of Sciences (India)

    Rosenani A Haque; M A Salam


    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.

  1. Growth, spectral, optical, thermal, crystallization perfection and nonlinear optical studies of novel nonlinear optical crystal—Urea thiosemicarbazone monohydrate (United States)

    Hanumantharao, Redrothu; Kalainathan, S.; Bhagavannarayana, G.


    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.

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

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


    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)(2)Ru(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 - 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.


    Directory of Open Access Journals (Sweden)

    Sulekh Chandra


    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

  4. Crystal structure of (E)-N 1-[(anthracen-9-yl)methyl­idene]-N 4-phenyl­benzene-1,4-di­amine (United States)

    Ahmad, Musheer; Golenya, Irina A.


    The title compound, C27H20N2, a Schiff base synthesized via a condensation reaction between anthracene-9-carbaldehyde and N-phenyl-p-phenyl­enedi­amine, crystallizes with three independent mol­ecules in the asymmetric unit. The three mol­ecules have slightly varying overall conformations, all having trans conformations with respect to the C=N bond. In the crystal, the packing features N—H⋯N hydrogen bonds, which connect mol­ecules into chains extending along the c-axis direction, inter­linked by C—H⋯π inter­actions (minimum H⋯Cg = 2.65 Å) into sheets lying parallel to (001). PMID:28217328

  5. Allosteric interaction of the anticholinergic drug [N-(4-phenyl)-phenacyl-l-hyoscyamine] (Phenthonium) with nicotinic receptors of post-ganglionic sympathetic neurons of the rat vas deferens. (United States)

    Munhoz, Egberto; De Lima, Thereza C M; Souccar, Caden; Lapa, Antonio J; Lima-Landman, Maria Teresa R


    Phenthonium (Phen), a quaternary analog of hyoscyamine, is a blocker of muscarinic activity and an allosteric blocker of alpha(1)2betagammaepsilon nicotinic receptors. Specifically, Phenthonium increases the spontaneous release of acetylcholine at the motor endplate without depolarizing the muscle or inhibiting cholinesterase activity. This paper compares Phenthonium's effects on sympathetic transmission and on ganglionic nicotinic receptor activation. Neurotransmitter release and twitch of the rat vas deferens were induced either by electrical stimulation or by 1,1-dimethyl-4-phenylpiperazine (DMPP) activation of nicotinic receptors. Contractions independent of transmitter release were induced by noradrenaline and adenosine 5'-triphosphate (ATP). Phenthonium inhibited transmitter release and depressed twitch without changing the responsiveness to noradrenaline or ATP. Twitch depression did not occur after K(+)-channel blockade with 4-aminopyridine (4-AP) or charybdotoxin. DMPP had a similar effect, but high concentrations induced contraction of non-stimulated organs. Incubation of Phenthonium inhibited further DMPP twitch depression and non-competitively depressed the contractile responses elicited by DMPP. Furthermore, mecamylamine, but neither methyllycaconitine nor atropine, blocked the contraction elicited by DMPP. Phenthonium and DMPP are K(+)-channel openers that primarily inhibit sympathetic transmission. Contraction induced by DMPP was probably mediated by neuronal nicotinic receptor other than the alpha7 subtype. The blockade of DMPP contractile response was unrelated to Phenthonium's antimuscarinic or K(+)-channel opening activities. Since Phenthonium's quaternary chemical structure limits its membrane diffusion, the non-competitive inhibition of DMPP excitatory responses should be linked to allosteric interaction with neuronal nicotinic receptors that putatively qualify Phenthonium as a novel modulator of cholinergic synapses.

  6. 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. (United States)

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


    Thiosemicarbazones such as Triapine (Tp) and Dp44mT are tridentate iron (Fe) chelators that have well-documented antineoplastic activity. Although 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 reductase (GR) have this activity and that there is considerable specificity to the interactions between specific redox centers in these enzymes and various Fe(III) complexes. Site-directed variants of TrxR1 demonstrate that the selenocysteine (Sec) of the enzyme is not required, whereas the C59 residue and the flavin have important roles. Although TrxR1 and GR have analogous C59/flavin motifs, TrxR is considerably faster than GR. For both enzymes, Fe(III)(Tp)2 is reduced faster than Fe(III)(Dp44mT)2. This reduction promotes redox cycling and the generation of hydroxyl radical (HO) in a peroxide-dependent manner, even with low-micromolar levels of Fe(Tp)2. TrxR also reduces Fe(III)-bleomycin and this activity is Sec-dependent. TrxR cannot reduce Fe(III)-EDTA at significant rates. Our findings are the first to demonstrate pro-oxidant reductive activation of Fe(III)-based antitumor thiosemicarbazones by interactions with specific enzyme species. The marked elevation of TrxR1 in many tumors could contribute to the selective tumor toxicity of these drugs by enhancing the redox activation of Fe(III)-thiosemicarbazones and the generation of reactive oxygen species such as HO.

  7. Cinnamaldehyde and cuminaldehyde thiosemicarbazones and their copper(II) and nickel(II) complexes: a study to understand their biological activity. (United States)

    Bisceglie, Franco; Pinelli, Silvana; Alinovi, Rossella; Goldoni, Matteo; Mutti, Antonio; Camerini, Alessandro; Piola, Lorenzo; Tarasconi, Pieralberto; Pelosi, Giorgio


    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.

  8. Antitumor Metallothiosemicarbazonate:Synthesis,Crystal Structure,Spectra and Antitumor Studies of Co(Ⅲ) Complex with Thiosemicarbazone Derivative of 2-Benzoylpyridine

    Institute of Scientific and Technical Information of China (English)

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


    The title complex[Co(L)2]Cl·4H2O I has been achieved via self-assembly by incorporating cobalt into 2-benzoylpyridine thiosemicarbazonate ligand,and characterized by elemental analysis,infrared spectra,mass spectra and single-crystal X-ray diffraction study.The crystal crystallizes in monoclinic,space group P21/n,with a=10.227(3),b=17.363(4),c=17.459(4)(A),β=100.408(4)°,V=3049.2(13)(A)3,z=4,Mr=677.08,Dc=1.475 g/cm3,μ(MoKα)=0.834 mm-1,F(000)=1400,the final R=0.0747 and wR=0.0896 for 1663 observed reflections with Ⅰ>2σ(Ⅰ).The complex contains one six-coordinated cobalt ion connected by two thiosemicarbazone ligands which act as a tridentate ligand to coordinate with the center metal atoms via two pyridyl nitrogen atoms,two imine nitrogen atoms and two sulfur atoms giving rise to a mononuclear structure.Hydrogen bonds existing in the complex link the different components to stabilize the crystal structure.The antitumor activity of the title complex Was tested against A549 lung cancer cell line.Complex Ⅰ exhibits antitumor activity.

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

    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


    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.

  10. Pterostilbene carboxaldehyde thiosemicarbazone, a resveratrol derivative inhibits 17β-Estradiol induced cell migration and proliferation in HUVECs. (United States)

    Nikhil, Kumar; Sharan, Shruti; Wishard, Rohan; Palla, Srinivasa Rao; Krishna Peddinti, Rama; Roy, Partha


    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.

  11. Effects of butane-2,3-dione thiosemicarbazone oxime on testicular damage induced by cadmium in mice. (United States)

    de Freitas, Mayara Lutchemeyer; Dalmolin, Laíza; Oliveira, Lia Pavelacki; da Rosa Moreira, Laís; Roman, Silvane Souza; Soares, Félix Alexandre Antunes; Bresolin, Leandro; Duarte, Marta Maria Medeiros Frescura; Brandão, Ricardo


    Our group of studies investigated the action of butane-2,3-dione thiosemicarbazone oxime against the testicular damage caused by cadmium chloride (CdCl(2)) in mice. Mice received a single injection of CdCl(2 )(5 mg/kg, intraperitoneally) and, after thirty minutes, the oxime (10 mg/kg, subcutaneously) was administered. Twenty four hours after the last administration, the animals were killed by cervical dislocation and the testes and serum were removed for analysis. The parameters determined were δ-aminolevulinate dehydratase (δ-ALA-D), myeloperoxidase (MPO), glutathione-S-transferase (GST) and glutathione peroxidase (GPx) activities. The levels of thiobarbituric acid-reactive substances (TBARS), nonprotein thiols (NPSH), ascorbic acid, cadmium and testosterone were also determined. In addition, histological analysis and cytokines quantification (IL-1, IL-6, IL-10, TNF-α and IFN-γ) were performed. Our results demonstrated that the oxime was effective in restoring the inhibition in δ-ALA-D activity induced by CdCl(2). The activation of MPO and increase in IL-1, IL-6, TNF-α and IFN-γ levels induced by CdCl(2) were also reduced by oxime. IL-10, which was reduced by cadmium, was restored by oxime administration. In addition, the oxime was effective in restoring the increase in TBARS levels and the reduction on NPSH levels induced by CdCl(2). Our results demonstrated that oxime was effective in containing the histological alterations induced by CdCl(2). In addition, oxime was able to increase the testosterone levels, reduced by cadmium exposure. In conclusion, the oxime tested was effective in reducing the testicular damage induced by CdCl(2) in mice. The beneficial effects of this oxime are related to its antioxidant and anti-inflammatory action.

  12. 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

    Indian Academy of Sciences (India)



    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.


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    Ludmila Chiriac


    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.

  14. 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

    Directory of Open Access Journals (Sweden)

    Dr.Mohammed.Fakruddin Ali Ahmed


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  16. Synthesis of Co9S8 and CoS nanocrystallites using Co(II) thiosemicarbazone complexes as single-source precursors

    Indian Academy of Sciences (India)

    Amol S Pawar; Shivram S Garje


    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.


    Directory of Open Access Journals (Sweden)

    Vasilii GRAUR


    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.

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

    Directory of Open Access Journals (Sweden)

    C.S. Carvalho


    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.

  19. 4-Methylbenzaldehyde thiosemicarbazone

    Directory of Open Access Journals (Sweden)

    Jian Zhang


    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.

  20. Benzaldehyde thiosemicarbazone monohydrate

    Directory of Open Access Journals (Sweden)

    Sheng-Jiu Gu


    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.

  1. Simultaneous spectrophotometric determination of copper, cobalt, nickel and iron in foodstuffs and vegetables with a new bis thiosemicarbazone ligand using chemometric approaches. (United States)

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


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

  2. Concomitant Effects of Transition Metal Chelation and Solvent Polarity on the First Molecular Hyperpolarizability of 4-Methoxyacetophenone Thiosemicarbazone: A DFT Study

    Directory of Open Access Journals (Sweden)

    Nyiang Kennet Nkungli


    Full Text Available Nonlinear optical (NLO properties of organic and metal-organic materials are of considerable interest to emerging optoelectronic and photonic technologies. Much work has been carried out on the former materials but the latter ones have received less attention till date. Herein, a density functional theory (DFT study on the combined effects of transition metal chelation and solvent polarity on the first hyperpolarizability (βtot of 4-methoxyacetophenone thiosemicarbazone (MAPTSC is reported. MAPTSC exhibits a tautomeric form with higher optical nonlinearity rendering its NLO response in polar solvents potentially switchable. Our results have revealed significant modifications of the first hyperpolarizability of MAPTSC upon complexation with different transition metal chlorides in the presence of solvents with varying dielectric constants. Therefore, its second-order NLO response is highly tunable by the synergy of transition metal chelation and solvent polarity. MAPTSC and its Zn(II and Pt(II chloride complexes are promising NLO materials because their gas-phase βtot values are larger than those of the prototype push-pull molecules, para-nitroaniline (PNA and urea, by factors of about 1.40–1.76 and 19.57–37.24, respectively; these factors greatly increase in polar solvent medium. Moreover, they possess high optical transparencies in the visible region of the electromagnetic spectrum which mitigate transparency/nonlinearity trade-offs, thereby increasing the likelihood of broad band NLO response.

  3. 4-Nitrobenzaldehyde thiosemicarbazone: a new compound derived from S-(-)-limonene that induces mitochondrial alterations in epimastigotes and trypomastigotes of Trypanosoma cruzi. (United States)

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


    Trypanosoma cruzi is the causative agent of Chagas' disease, a parasitic disease that remains a serious health concern with unsatisfactory treatment. Drugs that are currently used to treat Chagas' disease are partially effective in the acute phase but ineffective in the chronic phase of the disease. The aim of the present study was to evaluate the antitrypanosomal activity and morphological, ultrastructural and biochemical alterations induced by a new molecule, 4-nitrobenzaldehyde thiosemicarbazone (BZTS), derived from S-(-)-limonene against epimastigote, trypomastigote and intracellular amastigote forms of T. cruzi. BZTS inhibited the growth of epimastigotes (IC50 = 9·2 μ m), intracellular amastigotes (IC50 = 3·23 μ m) and inhibited the viability of trypomastigotes (EC50 = 1·43 μ m). BZTS had a CC50 of 37·45 μ m in LLCMK2 cells. BZTS induced rounding and distortion of the cell body and severely damaged parasite mitochondria, reflected by extensive swelling and disorganization in the inner mitochondrial membrane and the presence of concentric membrane structures inside the organelle. Cytoplasmic vacuolization, endoplasmic reticulum that surrounded organelles, the loss of mitochondrial membrane potential, and increased mitochondrial O2 •- production were also observed. Our results suggest that BZTS alters the ultrastructure and physiology of mitochondria, which could be closely related to parasite death.

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

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    Felipe S. Pessoto


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

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

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


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


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    Prabhakar S. Navarkar


    Full Text Available Acetophenone 2’,5’-dihydroxy thiosemicarbazone (ADHTS is proposed as a new sensitive and selective reagent for the Spectrophotometric determination of trace amount of Iron. The optimum extraction conditions were evaluated by studying various parameters like pH, solvent, reagent concentration, equilibration time and stability of extracted complex. The reagent reacts with Iron to form a yellow colored 1:2 chelate, at the pH 3.6.The complex is extracted in n-Butanol. The absorption spectrum shows maxima at 430 nm. Beer’s law is obeyed in the concentration range 1 to 8 ppm for Iron. The molar absorptivity is 646.06 L mol-1cm–1 and Sandell’s sensitivity is 0.0869μg cm-2 The Limit of Detection for the proposed method was found to be 0.561 ppm. The proposed method is highly sensitive, selective, simple, rapid, accurate, and has been satisfactorilyapplied for the determination of Iron in the synthetic mixtures, and real samples.

  7. Preparation,Characterization and Crystal Structure Determination of a Nickel Complex[Ni(ftsc)2NO3]NO3(Hftsc=Furan-2-carbaldehyde Thiosemicarbazone)

    Institute of Scientific and Technical Information of China (English)

    BAI Yan; PAN Xiao-Jing; DANG Dong-Bin; JIN Ya-Nan; WANG Jing-Ping


    A new Ni(Ⅱ)complex,[Ni(ftsc)2NO3]NO3(Hftsc=furan-2-carbaldehyde thiosemicarbazone),has been synthesized and characterized by IR,UV spectra and single-crystal X-ray diffraction analysis.It crystallizes in a monoclinic system,space group P21/n,with a=10.5203(13),b=9.2094(11),c=20.829(3)(A),β=91.518(2)°,V=2017.3(5)(A)3,Z=4,F(000)=1064,Dc=1.716 g/cm3,and wR=0.0800.The complex contains a six-coordinated nickel(Ⅱ)center which is bound to two imine nitrogen atoms and two thiolato sulfur atoms of two ligands as well as two oxygen atoms from a nitrate anion to assume a distorted octahedral coordination geometry.In addition,intermolecular N-H…O and C-H…O hydrogen bonds between adjacent molecules link the molecules together to form a three-dimensional structure.

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

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


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

  9. Effects on rat testes of the thiosemicarbazone derivative Schiff base (4-(1-phenylmethylcyclobutane-3-yl)-2-(2-hydroxybenzylidenehydrazino)thiazole) and its cadmium(II) complex. (United States)

    Oner, Hakan; Karatepe, Mustafa; Karatas, Fikret; Oner, Jale; Yilmaz, Ibrahim; Cukurovali, Alaaddin


    The aim of this study was to investigate structural and biochemical changes in testes of rats treated with the thiosemicarbazone derivative thiazole ring Schiff base, (4-(1-phenyl-methylcyclobutane-3-yl)-2-(2-hydroxybenzylidene-hydrazino) thiazole (L), and its Cd(II) complex (CdL(2)). The animals were divided into three groups. Group I was designated as control. The rats in groups II and III were injected subcutaneously with L or CdL(2) respectively at 150-mg kg(-1) doses at 3-day intervals for 15 days. At the end of the study, blood samples were collected for biochemical analysis, and testes were removed for histological examinations. Serum levels of vitamin A, E and MDA of the L-injected group were similar to the control group. While CdL(2) treatment decreased serum vitamin A and E levels, it increased the MDA level compared to other groups. Histologically, the testes structures of L-treated animals were similar to the control. Spermatogenic cells in seminiferous tubules of CdL(2)-treated animals displayed necrosis. Nuclei of spermatogonia and primary spermatocytes were pyknotic and heterochromatic. Homogenous pink particles were present in place of the spermatids. The interstitial areas were oedematous and intertubular vessels were plugged. In conclusion, the present results indicate that L does not cause biochemical and morphological alterations, but its Cd(II) complex has degenerative effects in normal rat testes.

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

    Sampath, Krishnan; Sathiyaraj, Subbaiyan; Jayabalakrishnan, Chinnasamy


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

  11. Mixed ligand ruthenium(III) complexes of benzaldehyde 4-methyl-3-thiosemicarbazones with triphenylphosphine/triphenylarsine co-ligands: Synthesis, DNA binding, DNA cleavage, antioxidative and cytotoxic activity (United States)

    Sampath, K.; Sathiyaraj, S.; Raja, G.; Jayabalakrishnan, C.


    The new ruthenium(III) complexes with 4-methyl-3-thiosemicarbazone ligands, (E)-2-(2-chlorobenzylidene)-N-methylhydrazinecarbothioamide (HL1) and (E)-2-(2-nitrobenzylidene)-N-methylhydrazinecarbothioamide (HL2), were prepared and characterized by various physico-chemical and spectroscopic methods. The title compounds 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 ligands and complexes were investigated by absorption spectroscopy and IR spectroscopy. It reveals that the compounds bind to nitrogenous bases of DNA via intercalation. The oxidative cleavage of the complexes with CT-DNA inferred that the effects of cleavage are dose dependent. Antioxidant study of the ligands and complexes showed 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.

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

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


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

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

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


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

  14. Acid–base equilibria of the Zn(II and Fe(III complexes with condensation products of 2-acetylpyridine and the dihydrazide of oxalic and malonic acid

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    Full Text Available Acid–base equilibria of Zn(II and Fe(III complexes with N',N'2-bis[(1E-1-(2-pyridylethylidene]ethanedihydrazide (ligand L1 and N',N'2-bis[(1E-1-(2-pyridylethylidene]propanedihydrazide (ligand L2, i.e., [Fe(L1Cl2(H2O], [Fe(L2Cl(H2O]2+, [Zn(L1(H2O3]+ and [Zn(L2(H2O2]2+, which expressed cytotoxic activity, were investigated in aqueous media. The equilibrium constants were determined potentiometrically at 25 °C at a constant ionic strength of 0.10 mol/dm3 (Na2SO4. The results showed that at pH < 8 both the Fe(III complexes studied here have three, while [Zn(L1(H2O3]+ and [Zn(L2(H2O2]2+ have one and two titratable protons, respectively. Based on the obtained values for the equilibrium constants, protonation schemes of the examined complexes are proposed.

  15. Metal complexes of 3-(4-bromophenyl)-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone: cytotoxic activity and investigation on the mode of action of the gold(III) complex. (United States)

    Sâmia, Luciana B P; Parrilha, Gabrieli L; Da Silva, Jeferson G; Ramos, Jonas P; Souza-Fagundes, Elaine M; Castelli, Silvia; Vutey, Venn; Desideri, Alessandro; Beraldo, Heloisa


    Complexes [Au(PyCT4BrPh)Cl]Cl (1), [Pt(PyCT4BrPh)Cl]0.5KCl (2), and [Pd(PyCT4BrPh)Cl]KCl (3) were obtained with 3-(4-bromophenyl)-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone (HPyCT4BrPh). Although complexes (2) and (3) did not exhibit potent cytotoxic activity, HPyCT4BrPh and its gold(III) complex (1) proved to be highly cytotoxic against HL-60 (human promyelocytic leukemia) and THP-1 (human monocytic leukemia) cells, and against MDA-MB 231 and MCF-7 (human breast adenocarcinoma) solid tumor cells. Except for HL-60 cells, upon coordination to gold(III) a 2- to 3-fold increase in the cytotoxic effect was observed. An investigation on the possible biological targets of the gold(III) complex was carried out. Complex (1) but not the free thiosemicarbazone inhibits the enzymatic activity of thioredoxin reductase (TrxR). The affinity of 1 for TrxR suggests metal binding to a selenol residue in the active site of the enzyme. While HPyCT4BrPh was inactive, 1 was able to inhibit topoisomerase IB (Topo IB) activity. Hence, inhibition of TrxR and Topo IB could contribute to the mechanism of cytotoxic action of complex (1).

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

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


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

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

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


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

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

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    Sriram D


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

  19. Development of a highly sensitive extractive spectrophotometric method for the determination of nickel(II) from environmental matrices using N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone. (United States)

    Ramachandraiah, C; Rajesh Kumar, J; Janardhan Reddy, K; Lakshmi Narayana, S; Varada Reddy, A


    Nickel(II) reacts with N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone (ECCT) and forms a yellow colored complex, which was extracted into n-butanol from sodium acetate and acetic acid buffer at pH 6.0. The absorbance value of the Ni(II)-ECCT complex was measured at different intervals of time at 400 nm, to ascertain the time stability of the complex. The extraction of the complex into the solvent was instantaneous and stable for more than 72 h. The system obeyed Beer's law in the concentration range of 1.2-5.6 microg ml(-1) of nickel(II), with an excellent linearity and a correlation coefficient of 0.999. The molar absorptivity and Sandell's sensitivity of the extracted species were found to be 1.114 x 10(4)L mol(-1)cm(-1) and 5.29 x 10(-3)microg cm(-2) at 400 nm, respectively. Hence, a detailed study of the extraction of nickel(II) with ECCT has been undertaken with a view to developing a rapid and sensitive extractive spectrophotometric method for the determination of nickel(II) when present alone or in the presence of diverse ions which are usually associated with nickel(II) in environmental matrices like soil and industrial effluents. Various standard alloy samples (CM 247 LC, IN 718, BCS 233, 266, 253 and 251) have been tested for the determination of nickel for the purpose of validation of the present method. The results of the proposed method are comparable with those from atomic absorption spectrometry and were found to be in good agreement.

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

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


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

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

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    Eliana F Castro

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

  2. Synthesis, structure and antifungal activity of thiophene-2,3-dicarboxaldehyde bis(thiosemicarbazone) and nickel(II), copper(II) and cadmium(II) complexes: unsymmetrical coordination mode of nickel complex. (United States)

    Alomar, Kusaï; Landreau, Anne; Allain, Magali; Bouet, Gilles; Larcher, Gérald


    The reaction of nickel(II), copper(II) chlorides and cadmium(II) chloride and bromide with thiophene-2,3-dicarboxaldehyde bis(thiosemicarbazone) (2,3BTSTCH2) leads to a series of new complexes: [Ni(2,3BTSTCH)]Cl, [Cu(2,3BTSTC)], [CdCl2(2,3BTSTCH2)] and [CdBr2(2,3BTSTCH2)]. The crystal structures of the ligand and of [Ni(2,3BTSTCH)]Cl complex have been determined. In this case, we remark an unusual non-symmetrical coordination mode for the two functional groups: one acting as a thione and the second as a deprotonated thiolate. All compounds have been tested for their antifungal activity against human pathogenic fungi: Candida albicans, Candida glabrata and Aspergillus fumigatus, the cadmium complexes exhibit the highest antifungal activity. Cytotoxicity was evaluated using two biological methods: human MRC5 cultured cells and brine shrimp Artemia salina bioassay.

  3. Solid phase extraction of Cd, Cu, and Ni from leafy vegetables and plant leaves using amberlite XAD-2 functionalized with 2-hydroxy-acetophenone-thiosemicarbazone (HAPTSC) and determination by inductively coupled plasma atomic emission spectroscopy. (United States)

    Rao, G Purna Chandra; Seshaiah, Kalluru; Rao, Yerra Koteswara; Wang, M C


    A method for solid phase extraction of trace metals, namely, Cd, Cu, and Ni, using Amberlite XAD-2 functionalized with a new chelating ligand, 2-hydroxy-acetophenone-3-thiosemicarbazone (Amberlite XAD-2-HAPTSC), has been developed. The optimum experimental conditions for the quantitative sorption of three metals, pH, effect of flow rate, concentration of eluent, sorption capacity, kinetics of sorption, and the effect of diverse ions on the sorption of analytes have been investigated. The chelating resin could be reused for more than 20 cycles of sorption-desorption without any significant change (<1.5%). The accuracy of the proposed procedure was evaluated by standard reference materials. The proposed method was applied for the determination of trace metal ions in leafy vegetable samples collected from different sources and medicinal plant leaves.

  4. Corrosion inhibition of 6061 Al-15 vol. pct. SiC(p) composite and its base alloy in a mixture of sulphuric acid and hydrochloric acid by 4-(N,N-dimethyl amino) benzaldehyde thiosemicarbazone

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    Pinto, Geetha Mable [Department of Chemistry, National Institute of Technology Karnataka, Surathkal, Srinivasnagar 575 025, Mangalore, Karnataka (India); Nayak, Jagannath [Department of Metallurgical and Materials Engineering, National Institute of Technology Karnataka, Surathkal, Srinivasnagar 575 025, Karnataka (India); Shetty, A. Nityananda, E-mail: [Department of Chemistry, National Institute of Technology Karnataka, Surathkal, Srinivasnagar 575 025, Mangalore, Karnataka (India)


    Research highlights: {yields} Corrosion inhibition of Al-SiC composite. {yields} DMABT as corrosion inhibitor. {yields} Inhibition through physisorption of DMABT. - Abstract: The corrosion inhibition characteristics of 4-(N,N-dimethylamino) benzaldehyde thiosemicarbazone (DMABT) on the corrosion behavior of 6061 Al-15 vol. pct. SiC(p) composite and its base alloy were studied at different temperatures in acid mixture medium containing varying concentrations of hydrochloric acid and sulphuric acid using Tafel extrapolation technique and ac impedance spectroscopy (EIS). The effect of inhibitor concentration, temperature and concentration of the acid mixture media on the inhibitor action was investigated. It was found that inhibition efficiencies increase with the increase in inhibitor concentration, but decrease with the increase in temperature and with the increase in concentration of the acid media. Thermodynamic parameters for dissolution process were determined. The adsorption of DMABT on both the composite and base alloy was found to be through physisorption obeying Freundlich adsorption isotherm.

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

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


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

  6. Second-order Optical Nonlinearity of the ⅡB - Group Complexes from Thiosemicarbazone Derivative%ⅡB族氨基硫脲衍生配合物的二阶非线性光学性质

    Institute of Scientific and Technical Information of China (English)

    田玉鹏; 吴杰颖; 张胜义; 马文; 李胜利; 谢复新


    设计合成了三种含三种不同取代基(-N(CH3)2,-OCH3,-NO2)氨基硫脲衍生物配体及其ⅡB族配合物M(Ⅱ)X2L2(M=Zn,Cd;X=Cl,Br,I),并通过元素分析和IR光谱进行了表征。测试了它们的粉末SHG效应。在此基础上结合理论计算和以前的工作,讨论了该类配合物产生SHG效应的微观原因。最后,对NLO(nonlinear optical)配合物的分子设计及配合物产生宏观微观NLO效应的联系进行了探讨。%Three kinds of ligands were designed. The ligands are derivatives from thiosemicarbazone, and with different benzaldehyde containing - N(CH3)2, - OCH3, - NO2 group, which abbreviated as L1, L2, L3, respectively. The three new thiosemicarbazone derivative ligands and their ⅡB group complexes M(Ⅱ)X2 L2(M=Zn, Cd;X=Cl, Br, I) were also synthesized in this work. The complexes have been characterized by spectroscopic techniques and elemental analysis. At last, general guidance for the molecular design of metal complexes for nonlinear optics was postulated based on second harmonic generation powder determination and theoretical calculation.

  7. N4-phenyl modifications of N2-(2-hydroxyl)ethyl-6-(pyrrolidin-1-yl)-1,3,5-triazine-2,4-diamines enhance glucocerebrosidase inhibition by small molecules with potential as chemical chaperones for Gaucher disease. (United States)

    Huang, Wenwei; Zheng, Wei; Urban, Daniel J; Inglese, James; Sidransky, Ellen; Austin, Christopher P; Thomas, Craig J


    A series of 1,3,5-triazine-2,4,6-triamines were prepared and analyzed as inhibitors of glucocerebrosidase. Synthesis, structure activity relationships and the selectivity of chosen analogues against related sugar hydrolases enzymes are described.

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

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


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

  9. Thiosemicarbazones as Aedes aegypti larvicidal. (United States)

    da Silva, João Bosco P; Navarro, Daniela Maria do A F; da Silva, Aluizio G; Santos, Geanne K N; Dutra, Kamilla A; Moreira, Diogo Rodrigo; Ramos, Mozart N; Espíndola, José Wanderlan P; de Oliveira, Ana Daura T; Brondani, Dalci José; Leite, Ana Cristina L; Hernandes, Marcelo Zaldini; Pereira, Valéria R A; da Rocha, Lucas F; de Castro, Maria Carolina A B; de Oliveira, Beatriz C; Lan, Que; Merz, Kenneth M


    A set of aryl- and phenoxymethyl-(thio)semicarbazones were synthetized, characterized and biologically evaluated against the larvae of Aedes aegypti (A. aegypti), the vector responsible for diseases like Dengue and Yellow Fever. (Q)SAR studies were useful for predicting the activities of the compounds not included to create the QSAR model as well as to predict the features of a new compound with improved activity. Docking studies corroborated experimental evidence of AeSCP-2 as a potential target able to explain the larvicidal properties of its compounds. The trend observed between the in silico Docking scores and the in vitro pLC50 (equals -log LC50, at molar concentration) data indicated that the highest larvicidal compounds, or the compounds with the highest values for pLC50, are usually those with the higher docking scores (i.e., greater in silico affinity for the AeSCP-2 target). Determination of cytotoxicity for these compounds in mammal cells demonstrated that the top larvicide compounds are non-toxic.

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

    Directory of Open Access Journals (Sweden)

    Elena Pahonțu


    Full Text Available New Cu(II, Pd(II and Pt(II complexes, (Cu(L(H2O2(OAc (1, (Cu(HL(H2O2(SO4 (2, (Cu(L(H2O2(NO3 (3, (Cu(L(H2O2(ClO4 (4, (Cu(L2(H2O2 (5, (Pd(L(OAcH2O (6, and (Pt(L2 (7 were synthesized from 8-ethyl-2-hydroxytricyclo(,7tridecan-13-one thiosemicarbazone (HL. The ligand and its metal complexes were characterized by IR, 1H-NMR, 13C-NMR, UV-Vis, FAB, EPR, mass spectroscopy, elemental and thermal analysis, magnetic susceptibility measurements and molar electric conductivity. The free ligand and the metal complexes have been tested for their antimicrobial activity against E. coli, S. enteritidis, S. aureus, E. faecalis, C. albicans and cytotoxicity against the NCI-H1573 lung adenocarcinoma, SKBR-3 human breast, MCF-7 human breast, A375 human melanoma and HL-60 human promyelocytic leukemia cell lines. Copper complex 2 exhibited the best antiproliferative activities against MCF-7 human breast cancer cells. A significant inhibition of malignant HL-60 cell growth was observed for copper complex 2, palladium complex 6 and platinum complex 7, with IC50 values of 1.6 µM, 6.5 µM and 6.4 µM, respectively.

  11. 超声辐射下水溶液中离子液体催化合成芳醛缩氨基硫脲%Synthesis of aromatic aldehyde thiosemicarbazones catalyzed by ionic liquid in water under ultrasound irradiation

    Institute of Scientific and Technical Information of China (English)

    刘卉闵; 崔鹏雷; 魏俊萍; 张冬暖; 张英群


    A series of aromatic aldehyde thiosemicarbazones were synthesized by the condensation reactions of aromatic aldehydes with thiosemicarbazide in water with 3-methyl-l-(3-sulfopropyl)-imidazolium trifluoro acetate as catalyst under ultrasound irradiation.The yields were ranged from 60.0%-95.0%.The structures of the products were confirmed by 1HNMR spectroscopy,IR and elemental analysis.The Bronsted acidic ionic liquid could be recycled easily.It is shown that the proposed method is easy,efficient and environmental friendly.%在超声波辐射下水相中以酸性甲基咪唑丙烷磺酸-三氟乙酸离子液体催化芳醛和氨基硫脲进行反应,合成了系列芳醛缩氨基硫脲衍生物,产率为60.0%~95.0%.产物结构经1 HNMR,IR,元素分析表征,该反应具有反应时间短、产率高、环境友好、后处理方便、催化剂可回收重复使用的优点.

  12. 3-methylcyclohexanone thiosemicarbazone: determination of E/Z isomerization barrier by dynamic high-performance liquid chromatography, configuration assignment and theoretical study of the mechanisms involved by the spontaneous, acid and base catalyzed processes. (United States)

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


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

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

    Directory of Open Access Journals (Sweden)



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

  14. Lysosomal membrane stability plays a major role in the cytotoxic activity of the anti-proliferative agent, di-2-pyridylketone 4,4-dimethyl-3-thiosemicarbazone (Dp44mT). (United States)

    Gutierrez, Elaine M; Seebacher, Nicole A; Arzuman, Laila; Kovacevic, Zaklina; Lane, Darius J R; Richardson, Vera; Merlot, Angelica M; Lok, Hiu; Kalinowski, Danuta S; Sahni, Sumit; Jansson, Patric J; Richardson, Des R


    The potent and selective anti-tumor agent, di-2-pyridylketone 4,4-dimethyl-3-thiosemicarbazone (Dp44mT), localizes in lysosomes and forms cytotoxic copper complexes that generate reactive oxygen species (ROS), resulting in lysosomal membrane permeabilization (LMP) and cell death. Herein, the role of lysosomal membrane stability in the anti-tumor activity of Dp44mT was investigated. Studies were performed using molecules that protect lysosomal membranes against Dp44mT-induced LMP, namely heat shock protein 70 (HSP70) and cholesterol. Up-regulation or silencing of HSP70 expression did not affect Dp44mT-induced LMP in MCF7 cells. In contrast, cholesterol accumulation in lysosomes induced by the well characterized cholesterol transport inhibitor, 3-β-[2-(diethyl-amino)ethoxy]androst-5-en-17-one (U18666A), inhibited Dp44mT-induced LMP and markedly and significantly (peffect of U18666A in increasing lysosomal cholesterol and preventing the cytotoxic activity of Dp44mT was not due to induced autophagy. Instead, U18666A was found to decrease lysosomal turnover, resulting in autophagosome accumulation. Moreover, preincubation with U18666A did not prevent the ability of Dp44mT to induce autophagosome synthesis, indicating that autophagic initiation via Dp44mT occurs independently of LMP. These studies demonstrate the significance of lysosomal membrane stability in relation to the ability of Dp44mT to execute tumor cell death and overcome pro-survival autophagy. Hence, lysosomal-dependent cell death induced by Dp44mT serves as an important anti-tumor strategy. These results are important for comprehensively understanding the mechanism of action of Dp44mT.

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

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


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

  16. A phase I and pharmacokinetic study of oral 3-aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP, NSC #663249) in the treatment of advanced stage solid cancers – A California Cancer Consortium Study (United States)

    Chao, Joseph; Synold, Timothy W.; Morgan, Robert J.; Kunos, Charles; Longmate, Jeff; Lenz, Heinz-Josef; Lim, Dean; Shibata, Stephen; Chung, Vincent; Stoller, Ronald G.; Belani, Chandra P.; Gandara, David R.; McNamara, Mark; Gitlitz, Barbara J.; Lau, Derick H.; Ramalingam, Suresh S.; Davies, Angela; Espinoza-Delgado, Igor; Newman, Edward M.; Yen, Yun


    Background 3-aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP) is a novel small molecule ribonucleotide reductase inhibitor. This study was designed to estimate the maximum-tolerated dose (MTD) and oral bioavailability of 3-AP in patients with advanced stage solid tumors. Methods Twenty patients received one dose of intravenous and subsequent cycles of oral 3-AP following a 3+3 patient dose-escalation. Intravenous 3-AP was administered to every patient at a fixed dose of 100 mg over a 2-hour infusion 1 week prior to the first oral cycle. Oral 3-AP was administered every 12 hours for 5 consecutive doses on days 1–3, days 8–10, and days 15–17 of every 28-day cycle. 3-AP was started at 50 mg with a planned dose escalation to 100, 150, and 200 mg. Dose-limiting toxicities (DLT) and bioavailability were evaluated. Results Twenty patients were enrolled. For dose level 1 (50mg), the second of three treated patients had a DLT of grade 3 hypertension. In the dose level 1 expansion cohort, three patients had no DLTs. No further DLTs were encountered during escalation until the 200 mg dose was reached. At the 200 mg 3-AP dose level, two treated patients had DLTs of grade 3 hypoxia. One additional DLT of grade 4 febrile neutropenia was subsequently observed at the de-escalated 150 mg dose. One DLT in 6 evaluable patients established the MTD as 150 mg per dose on this dosing schedule. Responses in the form of stable disease occurred in 5 (25%) of 20 patients. The oral bioavailability of 3-AP was 67 ± 29%, and was consistent with the finding that the MTD by the oral route was 33% higher than by the intravenous route. Conclusions Oral 3-AP is well-tolerated and has an MTD similar to its intravenous form after accounting for the oral bioavailability. Oral 3-AP is associated with a modest clinical benefit rate of 25% in our treated patient population with advanced solid tumors. PMID:22105720

  17. Synthesis and Antibacterial Activity Study of Glyoxal-bis-thiosemicarbazone and Its Metal Complexes%乙二醛双缩氨基硫脲及其金属配合物的合成和抑菌活性研究

    Institute of Scientific and Technical Information of China (English)

    何冰晶; 王幸南; 石云尧


    以氨基硫脲和乙二醛为原料合成了乙二醛双缩氨基硫脲及其与Mn(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)、Sr(Ⅱ)、Zn(Ⅱ)、Cu(Ⅱ)的金属配合物,通过核磁共振氢谱,红外光谱对配体和配合物进行表征,并测定了配体和配合物的生物活性.%Glyoxal-bis-thiosemicarbazone and its metal complexes of Mn, Co, Ni, Sr, Zn, Cu were synthesized using thiosemicarbazide and glyoxal as starting materials. Ligand and corresponding metal complexes are characterized through Nuclear Magnetic Resonance Hydrogen Spectrum and Infrared Spectrum, then their antibacterial activity are determined.

  18. Study of Kinetics of Complexation Reaction of Co2+ with 2-benzoylpyridine-4-phenyl-3-thiosemicarbazone and Kinetic spectrophotometric Determination of Cobalt%Co2+与BPPT络合反应动力学及动力学光谱法测定钴

    Institute of Scientific and Technical Information of China (English)

    BINGOL,Haluk; ATALAY,Tevfik


    Kinetics of complexation reaction of Co2+ with 2-benzoylpyridine-4-phenyl-3-thiosemicarbazone (BPPT)was spectrophotometrically examined at 421 nm. The ligand that is developed for a simple kinetic-spectrophotometric determination of Co2+ is based on 1:2 complex formation between Co2+ and BPPT. The complexation reaction was carried out in ethanol-water medium at 25 ℃. Kinetic and activation parameters of the complexation reaction were calculated, and the rate equation and the reaction mechanism were proposed. The calibration graph is linear in the concentration range of 0.10~2.91 mg·L-1 for the tangent method. The species that caused interference were investigated.

  19. Novel Zinc(II) Complexes [Zn(atc-Et)2] and [Zn(atc-Ph)2]: In Vitro and in Vivo Antiproliferative Studies (United States)

    Lopes, Erica de O.; de Oliveira, Carolina G.; da Silva, Patricia B.; Eismann, Carlos E.; Suárez, Carlos A.; Menegário, Amauri A.; Leite, Clarice Q. F.; Deflon, Victor M.; Pavan, Fernando R.


    Cisplatin and its derivatives are the main metallodrugs used in cancer therapy. However, low selectivity, toxicity and drug resistance are associated with their use. The zinc(II) (ZnII) thiosemicarbazone complexes [Zn(atc-Et)2] (1) and [Zn(atc-Ph)2] (2) (atc-R: monovalent anion of 2-acetylpyridine N4-R-thiosemicarbazone) were synthesized and fully characterized in the solid state and in solution via elemental analysis, Fourier transform infrared (FTIR), ultraviolet-visible (UV-Vis) and proton nuclear magnetic resonance (1H NMR) spectroscopy, conductometry and single-crystal X-ray diffraction. The cytotoxicity of these complexes was evaluated in the HepG2, HeLa, MDA-MB-231, K-562, DU 145 and MRC-5 cancer cell lines. The strongest antiproliferative results were observed in MDA-MB-231 and HepG2 cells, in which these complexes displayed significant selective toxicity (3.1 and 3.6, respectively) compared with their effects on normal MRC-5 cells. In vivo studies were performed using an alternative model (Artemia salina L.) to assure the safety of these complexes, and the results were confirmed using a conventional model (BALB/c mice). Finally, tests of oral bioavailability showed maximum plasma concentrations of 3029.50 µg/L and 1191.95 µg/L for complexes 1 and 2, respectively. According to all obtained results, both compounds could be considered as prospective antiproliferative agents that warrant further research. PMID:27213368

  20. Synthesis, characterization and thermal studies of binary and/or mixed ligand complexes of Cd(II), Cu(II), Ni(II) and Co(III) based on 2-(Hydroxybenzylidene) thiosemicarbazone: DNA binding affinity of binary Cu(II) complex. (United States)

    Saif, M; Mashaly, Mahmoud M; Eid, Mohamed F; Fouad, R


    A new series of metal complexes of Cd(II), Cu(II), Ni(II) and Co(III) with Schiff base ligand, H(2)L, 2-(Hydroxybenzylidene) thiosemicarbazone were synthesized. The mixed ligand complexes were prepared by using glycine (Gly), 2-aminopyridine (2-Ampy) and 1,10-phenanthroline (Phen) as secondary ligands. The structure of these complexes was identified and confirmed by elemental analysis, molar conductivity, UV-Vis, FT-IR and (1)H NMR spectroscopy and magnetic moment measurements as well as TG-DSC technique. The discussions of the prepared complexes indicate that the ligand behaves as a monoanionic tridentate ligand through ONS donor sites. Thermal studies suggested a mechanism for the degradation of the metal complexes as a function of temperature supporting the chelation modes and showed the possibility of obtaining new complexes pyrolytically in the solid state which cannot be synthesized from the solution. The absorption studies support that the binary Cu(II) complex exhibits a significant binding affinity to HS-DNA through intercalative mode.

  1. Investigation of the Lipophilicity of 2-Benzoylpyridine-Thiosemicarbazone Based on the Ion Transfer across the Liquid/Liquid Interface%液/液界面电子转移研究苯甲酰吡啶-缩氨基硫脲的亲脂性

    Institute of Scientific and Technical Information of China (English)

    AKGEMCI Emine G.; BINGOL Haluk; OZCELIK Mehmet; ERSOZ Mustafa


    The ion transfer reaction of 2-benzoylpyridine-thiosemicarbazone (HL), which has antimicrobial and antifungal properties and anticancer activity, has been studied to determine its lipophilicity by cyclic voltammetry at the water/1,2-dichloroethane (1,2-DCE) interface. The physicochemical parameters such as standard partition coefficient (IgP1) and the standard Gibbs energy of transfer (△G0,w→otr,I) of the protonated form of the ligand were measured as a function of pH in aqueous phase. The protonated form of the ligand exhibited reversible or quasi-reversible voltammograms at the 1,2-DCE in the range of pH 1-5. The protonation constants of the ligand, pKal, and pK? were determined spectrophotometrically and were found to be 12.14 and 3.24, respectively. The standard Gibbs energy of transfer (△G0,w→otr,N) and the partition coefficient of neutral species (IgPN) were also determined by the shake-flask method. The standard Gibbs energy of transfer of this compound across the water/1,2-DCE interface was evaluated as the quantitative measure of its lipophilicity. The difference between lgP1 and lgPN was related to the degree of charge delocalization and was used to evaluate qualitatively the lipophilicity of the ligand.

  2. Synthesis and biological activity of Cu(II),Ag(I), Cd(II)and Pd(II)complexes of betulinal thiosemicarbazone%桦木醛缩氨基硫脲铜、银、镉、钯金属配合物的合成及其生物活性研究

    Institute of Scientific and Technical Information of China (English)

    林汉; 刘颖; 朴凤玉; 韩荣弼


    Using combination principle,two betulinal thiosemicarbazone ligands and their Cu(II),Ag(I),Cd (II)and Pd(II)metal complexes were synthesized,which were characterized by IR,1 H NMR,TGA,MAL-DI-TOF and elemental analysis.The ligands and their metal complexes were evaluated for their antimicrobial activity and cytotoxicity.The results showed that the complex Ag (L1 )2 NO3 ·3H2 O has relatively good inhibitory effects on S.aureus 4220,S.mutans 3065 and E.coli 1924.Complexes Ag(L1 )2 NO3·3H2 O and Cu(L1 )2 Cl2 can significantly inhibit the viability of Hela cell.%运用拼合原理,合成了2种桦木醛缩氨基硫脲配体以及它们的铜、银、镉、钯金属配合物,运用红外光谱、核磁共振氢谱、热重分析、飞行质谱和元素分析方法对其进行了结构表征,并测试了配体和配合物的抑菌活性和细胞毒性.结果表明:配合物 Ag(L1)2 NO3·3H2 O 对 S.aureus 4220、S.mutans 3065和 E.coli 1924有较好的抑制作用;配合物 Ag(L1)2 NO3·3H2 O 和 Cu(L1)2 Cl2能够显著抑制 Hela 细胞的生存能力.

  3. Highly Selective Colorimetric Recognition of Copper Ions Based on N-Aryl Coumarin Methyl Ketone Thiosemicarbazone Receptors%N-芳基香豆素甲基酮缩氨基硫脲对Cu2+的选择性比色识别

    Institute of Scientific and Technical Information of China (English)

    魏太保; 李军舰; 林奇; 姚虹; 郭英; 白翠冰; 谢永强; 张有明


    设计合成了2种新型N-芳基香豆素甲基酮缩氨基硫脲受体分子S1和S2,利用紫外-可见(UV-Vis)吸收光谱考察了其对Fe3+,Hg2+,Ag+,Ca2+,Cu2+,Zn2+,Pb2+,Cd2+,Ni2+,Cr3+和Mg2+等阳离子的识别作用.结果表明,当加入Cu2+时,溶液颜色立刻由无色变为黄色,而加入其它阳离子则无变化,从而实现了对Cu2+的裸眼检测,具有专一选择性比色识别效果.通过计算可知,受体分子S2对Cu2+的络合常数大于S1,且主客体间形成1∶1的配合物.受体分子S2对Cu2+的检出限为2.0×10-7mol/L,稳定常数Ks=1.02×105 L/mol.另外,在EDTA存在时,配合物可以释放出Cu2+,与EDTA结合,表现出对Cu2+的“off-on”模式.%Two new A'-aryl coumarin methyl ketone thiosemicarbazone receptors were designed and synthesized. The binding properties of the receptors with cations such as Fe 3+ , Hg 2+ , Ag+ , Ca 2+ , Cu 2+, Zn 2+ , Pb 2+ , Cd2+, Ni2+, Cr3+ and Mg2+ in DMSO were investigated by UV-Vis spectroscopy. A clear color change from colorless to yellow was observed upon the addition of Cu 2+ to the solution of the two receptors in DMSO by naked-eyes and a single selectivity colorimetric recognition. The results showed that the two receptors had a better selectivity for Cu2+, but exhibited no evident binding with others cations. The data showed that the two receptors had different binding abilities with Cu2+. The UV-Vis data indicated that a 1 : 1 stoichiometry complex was formed between the receptor and Cu 2+. The detection limit of the sensor S2 toward Cu 2+ is 2. 0×l0~ mol/L and an association constant Ks of 1. 02×105 L/mol was measured. The sensing of Cu2+ by this sensor was found to be reversible, with the Cu2+-induced color being lost upon the addition of EDTA. The process of titrating sensor S2 with Cu2+ is reversible, and compound S2 could be used as an off-on switch chemosensor.

  4. Study of Thiosemicarbazone Derivative of Essential Fatty Acid



    Essential fatty acids results in numerous health benefits. Only two fatty acids are known to be essential for human alpha-linolenic acid (an omega-3 fatty acid) and linoleic acid (an omega-6 fatty acid).The importance of omega-3 fatty acids for physical well-being has been recognised for several decades . Omega-3 fatty acids have anti-inflammatory, antithrombotic, antiarrhythmic and hypolipidaemic effects. Cannabis sativa (Hemp) is an angiosperm belonging to the cannabaceae family and cannabi...

  5. Synthesis and antituberculosis activity of indole-pyridine derived hydrazides, hydrazide-hydrazones, and thiosemicarbazones. (United States)

    Velezheva, Valeriya; Brennan, Patrick; Ivanov, Pavel; Kornienko, Albert; Lyubimov, Sergey; Kazarian, Konstantin; Nikonenko, Boris; Majorov, Konstantin; Apt, Alexander


    We describe the design, synthesis, and in vitro antimycobacterial activity of a series of novel simple hybrid hydrazides and hydrazide-hydrazones combining indole and pyridine nuclei. The compounds are derivatives of 1-acetylindoxyl or substituted indole-3-carboxaldehydes tethered via a hydrazine group by simple C-N or double C=N bonds with 3- and 4-pyridines, 1-oxide 3- and 4-pyridine carbohydrazides. The most active of 15 compounds showed MICs values against an INH-sensitive strain of Mycobacterium tuberculosis H37Rv equal to that of INH (0.05-2 μg/mL). Five compounds demonstrated appreciable activity against the INH-resistant M. tuberculosis CN-40 clinical isolate (MICs: 2-5 μg/mL), providing justification for further in vivo studies.

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

    Directory of Open Access Journals (Sweden)

    Sinara Mônica Vitalino de Almeida


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

  7. Synthesis under Micromave Irradition and Crystal Structure of 4'-Acetylbenzo-15 -crown-5thiosemicarbazone

    Institute of Scientific and Technical Information of China (English)

    ZHANG You-ming; ZONG Guo-qiang; WEI Tai-bao


    The title compound is a bifunctional receptors including a thiourea group and a crown ether ring. Due to many possible potentials as a new class of reagents for membrane transports,ion-selective electrodes as well as reaction catalysts, the design and synthesis of bifunctional receptors for simultaneous binding of cations and anions is of ongoning interest in srprarnolecular chemistry1-5. In bifunctional receptors, the binding sites for anions and cations are covalently linked so as to exhibit allosteric or cooperative complexation where the binding affinity for anions(cations)is modified as a result of the cation(anion) complexation.Literature[6] reported that the ability of the thiourea group to bind anions is significantly enhanced when Na+ is bound to the crown moiety. To date, however only a few receptors of this class have been reported.6-8In this paper, we report an improved procedure under microwave irradiation that gives higher yields of title compound and needs fewer reaction times than traditional method.The structure of this compound was determined by IR ,element analysis and X-ray analysis.Scheme 1 The reaction equationThe crystal belongs to triclinic crystal system, P-1 space group, a=0.9547(0)nm, b=1.3637(3)nm,c=1.6029(3)nm, α =75.33(3) , β =83.62(3) , γ =70.99(3) ,Z=4,Dc=1.335g/cm3,F(000)=816,R1= 0.0557 ,wR2=0.1281. It is assembled into a three-dimensionalsupramolecule by intermolecular hydrogen bonds.

  8. Antiviral activity of Thiosemicarbazones derived from α-amino acids against Dengue virus. (United States)

    Padmanabhan, Padmapriya; Khaleefathullah, Sheriff; Kaveri, Krishansamy; Palani, Gunasekaran; Ramanathan, Giriprasath; Thennarasu, Sathiah; Tirichurapalli Sivagnanam, Uma


    The endemicity and seasonal outbreaks of Dengue disease in most tropical and subtropical countries underscores an urgent need to develop effective prevention and control measures. Development of a Dengue vaccine, which is complicated by the Antibody Dependent Enhancement effect (ADE), a viral inhibitor, seems prudent as it would inhibit the spread of the virus. In vitro methods such as MTT assay and plaque formation unit reduction assays were employed for screening the viral inhibitory property of α-amino acid based Thiosemicarbazides. The results elicits that at concentrations not exceeding the maximum non cytotoxic concentration (MNCC), these compounds completely prevented Dengue virus infection in vero cells as indicated by the absence of cytopathic effects in a dose-dependent manner. The high potency of Bz-Trp-TSC against all four types of Dengue virus infection elevates Thiosemicarbazide as a lead antiviral agent for Dengue disease. Screening small molecules for antiviral activity against the most rapidly spreading mosquito-borne viral disease is being explored by several research groups. Our findings would help to augment the efforts to identify the lead compounds for antiviral therapy to combat the Dengue disease. J. Med. Virol. 89:546-552, 2017. © 2016 Wiley Periodicals, Inc.

  9. Synthesis and Crystal Structural Characterization of a Thiosemicarbazone Derived from 4-Acylpyrazolone

    Institute of Scientific and Technical Information of China (English)

    LIU Guang-Fei; LIU Lang; HU Xin; JIA Dian-Zeng; YU Kai-Bei


    The reaction of 4-(p-fluobenzoyl)-2,5-dihydro-3-methyl-1-phenyl pyrazol-5-one with thiosemicarbazide in MeOH followed by recrystallization in EtOH gave rise to yellowish lamellar crystals of 4(p-fluo-α-aminothiocarbonyl hydrazonobenzal)-2,5-dihydro-3-methyl- 1 -phenyl pyrazol-5-one 1. It crystallizes in orthorhombic, space group Pbca with a = 18.445(4), b = 11.987(2),c = 19.249(4) (A), V= 4256.1(18) (A)3, Z = 8, Mr = 415.49, Dc= 1.297 g/cm3, T= 296(2) K, F(000) =1744, μ(MoKα) = 0.186 cm-1, R = 0.0521 and wR = 0.1211 for 1661 observed reflections with I >2σ(I). The compound was structurally characterized by elemental analyses, IR and 1H NMR. The intermolecular hydrogen bonds are present and a two-dimensional framework is formed by two intermolecular hydrogen bonds in the (001) plane.

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

    Directory of Open Access Journals (Sweden)

    M.S.T. Makki


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

  11. A Moessbauer investigation of complexes of tin tetrahalides with ambidentate Lewis bases containing nitrogen, sulphur and oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Teles, W.M. (Dept. de Quimica, ICEx, Univ. Federal de Minas Gerais, Belo Horizonte (Brazil)); Allain, L.R. (Dept. de Quimica, ICEx, Univ. Federal de Minas Gerais, Belo Horizonte (Brazil)); Filgueiras, C.A.L. (Dept. de Quimica, ICEx, Univ. Federal de Minas Gerais, Belo Horizonte (Brazil)); Abras, A. (Dept. de Fisica, ICEx, Univ. Federal de Minas Gerais, Belo Horizonte (Brazil))


    A series of 1 : 1 complexes was prepared with SnX[sub 4] (X = Cl, Br, I) and the Lewis bases 2-mercaptobenzothiazole, 2-mercapto-1-methylimidazole, 2-aminothiazole, 2-acetylpyridine, and 2,2'-bis(pyridyl)ketone. The latter two ligands yielded bidentate, N, O-bonded hexacoordinate complexes, whereas the other ligands produced monodentate, N-bonded pentacoordinate species, as suggested by Moessbauer parameters, which correlate quite well with the IR spectroscopy data. (orig.)

  12. A Mössbauer investigation of complexes of tin tetrahalides with ambidentate Lewis bases containing nitrogen, sulphur and oxygen (United States)

    Teles, Wagner M.; Allain, Leonardo R.; Filgueiras, Carlos A. L.; Abras, Anuar


    A series of 1 : 1 complexes was prepared with SnX4 (X=Cl, Br, I) and the Lewis bases 2-mercaptobenzothiazole, 2-mercapto-1-methylimidazole, 2-aminothiazole, 2-acetylpyridine, and 2,2'-bis(pyridyl)ketone. The latter two ligands yielded bidentate, N, O-bonded hexacoordinate complexes, whereas the other ligands produced monodentate, N-bonded pentaccoordinate species, as suggested by Mössbauer parameters, which correlate quite well with the IR spectroscopy data.

  13. Synthesis and Structure of 1.5Zn(phen)3·L·3NO3 Supramolecule (phen = o-Phenanthroline, L = 4-Aminoacetophenone Thiosemicarbazone)

    Institute of Scientific and Technical Information of China (English)

    ZHANG Nian-You; LI Quan-Jun; LIU Ying-Ying


    A supramolecular framework, 1.5Zn(phen)3·L·3NO3 (C63H48Zn1.5N16O9S), has been synthesized.The ligand L was synthesized by the condensation of p-aminoacetophenone with thiosemicarbazide.The crystal belongs to the monoclinic system, space group C2/c, with a = 31.005(2), b = 15.114(2), c = 24.887(3) -, β = 94.260(2)o, Z = 8, V = 11630(2) -3, Dc = 1.489 g/cm3, Mr = 1303.29, λ(MoKα) = 0.71069 -, μ = 0.735 mm-1, F(000) = 5368, Rint = 0.0699, R = 0.0505 and wR = 0.0707.Two independent Zn atoms are both coordinated by six N atoms from three phen ligands.π-π and C-H…π interactions among the L ligands and Zn(phen)3 cations, π-π and C-H…π interactions among the Zn(phen)3 cations and N-H…O hydrogen bonds among the L ligands and nitrate anions connect the whole structure into a 3-D supramolecular framework.

  14. Avaliação do potencial anticorrosivo de tiossemicarbazonas solubilizadas em microemulsão

    Directory of Open Access Journals (Sweden)

    Elaine Cristina M. de Moura


    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.


    Institute of Scientific and Technical Information of China (English)

    郭应臣; 钟国清; 栾绍嵘; 卓立宏


    @@ Schiff碱及其衍生物广泛地应用于化工生产和科学研究.水杨醛缩氨基硫脲Sc hiff碱的合成和结构已有报导[1],但通过X-射线粉末衍射指标化,确定其晶系和晶胞参数的工作未见报道,同样也没见报道D(+)-葡萄糖缩氨基硫脲的合成和结构表征.为了提高Schiff碱的水溶性和生物活性,我们合成了D(+)-葡萄糖缩氨基硫脲和水杨醛缩氨基硫脲,并对其进行了组成分析和结构表征.

  16. Synthesis, spectral characterization and biological evaluation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes with thiosemicarbazone ending by pyrazole and pyridyl rings (United States)

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


    Here we present the synthesis of the new Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes with chelating ligand (Z)-(2-((1,3-diphenyl-1H-pyrazol-4-yl)methylene) hydrazinyl)(pyridin-2-ylamino)methanethiol. All the complexes were characterized by elemental analysis, IR, 1H NMR, UV-vis, magnetic susceptibility measurements and EPR spectral studies. IR spectra of complexes showed that the ligand behaves as NN neutral bidentate, NSN mononegative tridentate and NSNN mononegative tetradentate. The electronic spectra and the magnetic measurements suggested the octahedral geometry for all complexes as well as the EPR confirmed the tetragonal distorted octahedral for Cu(II) complex. Cd(II) complex showed the highest inhibitory antioxidant activity either using ABTS method. The SOD-like activity exhibited those Cd(II) and Zn(II) complexes have strong antioxidative properties. We tested the synthesized compounds for antitumor activity and showed that the ability to kill liver (HePG2) and breast (MCF-7) cancer cells definitely.

  17. Synthesis and Crystal Structures of Copper(II) Complexes with Schiff Base Ligands: [Cu{sub 2}(acpy-mdtc){sub 2}(HBA)(ClO{sub 4})]·H{sub 2}O and [Cu{sub 2}(acpy-phtsc){sub 2}(HBA)]·ClO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Koo, Bon Kweon [Catholic Univ. of Daegu, Gyeongsan (Korea, Republic of)


    Two new Cu(II) complexes, [Cu{sub 2}(acpy-mdtc){sub 2}(HBA)(ClO{sub 4})]·H{sub 2}O (1) (acpy-mdtc{sup -} = 2-acetylpyridine S-methyldithiocarbamate and HBA{sup -} = benzilic acid anion) and [Cu{sub 2}(acpy-phtsc){sub 2}(HBA)]·ClO{sub 4} (2) (acpy-phtsc{sup -} = 2-acetylpyridine 4-phenyl-3-thiosemicarbazate) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. The X-ray analysis reveals that the structures of 1 and 2 are dinuclear copper(II) complexes bridged by two thiolate sulfur atoms of Schiff base ligand and bidentate bridging HBA{sup -} anion. For 1, each of the two copper atoms has different coordination environments. Cu1 adopts a five-coordinate square-pyramidal with a N{sub 2}OS{sub 2} donor, while Cu{sub 2} exhibits a distorted octahedral geometry in a N{sub 2}O{sub 2}S{sub 2} manner. For 2, two Cu(II) ions all have a five-coordinate square-pyramidal with a N{sub 2}OS{sub 2} donor. In each complex, the Schiff base ligand is coordinated to copper ions as a tridentate thiol mode.

  18. Crystal structure of 4-hydroxy-3-methoxybenzaldehyde 4-methylthiosemicarbazone methanol monosolvate

    Directory of Open Access Journals (Sweden)

    Adriano Bof de Oliveira


    Full Text Available In the title solvate, C15H15N3O2S·CH3OH, the thiosemicarbazone molecule is approximately planar; the maximum deviation from the mean plane is 0.4659 (14 Å and the dihedral angle between the aromatic rings is 9.83 (8°. This conformation is supported by an intramolecular N—H...N hydrogen bond. In the crystal, the thiosemicarbazone molecules are linked into dimers by pairs of N—H...S hydrogen bonds, thereby generating R22(8 loops. The methanol solvent molecule bonds to the thiosemicarbazone molecule through a bifurcated O—H...(O,O hydrogen bond and also accepts an O—H...O link from the thiosemicarbazone molecule. Together, these links generate a three-dimensional network.

  19. Synthesis and In Vitro and In Vivo Evaluation of a New 68Ga-Semicarbazone Complex: Potential PET Radiopharmaceutical for Tumor Imaging

    Directory of Open Access Journals (Sweden)

    N. S. Al-Hokbany


    Full Text Available In an attempt to develop new tumor imaging radiotracers with favorable biochemical properties, we have synthesized new 68Ga-2-acetylpyridine semicarbazone (68Ga-[APSC]2 as a potential positron emission tomography (PET tumor imaging agent using a straightforward and a one-step simple reaction. Radiochemical yield and purity were quantitative without HPLC purification. Biodistribution studies in nude mice model bearing human MDA-MB-231 cell line xenografts displayed significant tumor uptake of 68Ga-[APSC]2 radiotracer after 2 h postinjection (p.i.. The initial results demonstrate that 68Ga-[APSC]2 radiotracer may be useful probe for detecting and staging of hypoxic tumor using PET imaging modality.

  20. The simple production of nonsymmetric quaterpyridines through Kröhnke pyridine synthesis

    Directory of Open Access Journals (Sweden)

    Isabelle Sasaki


    Full Text Available Quaterpyridines have been demonstrated to be useful building blocks in metallo-supramolecular chemistry; however, their synthesis requires the preparation of sensitive building blocks. We present here three examples of nonsymmetric quaterpyridines that were easily obtained in yields of 70–85% by condensation of commercially available enones with 6-acetyl-2,2’:6’,2’’-terpyridine through a Kröhnke pyridine synthesis. Easy access to 6-acetyl-2,2’:6’,2’’-terpyridine starting from 2,6-diacetylpyridine and 2-acetylpyridine is described. The X-ray analysis of a chiral quaterpyridine and its Pt(II complex is presented.

  1. Structural and Spectroscopic Aspects of Schiff Base Metal Complexes of Cobalt(II, Nickel(II and Copper(II

    Directory of Open Access Journals (Sweden)

    B.K. Rai


    Full Text Available The complexes of Co(II, Ni(II and Cu(II with Schiff base 2-butyl thioquinazoline 4(3H thiosemicarbazone were synthesized. The general formulae of the complexes are of the type {M(L2X2], L=2 – butyl thioquinazoline 4(3H thiosemicarbazone; x = Cl-, Br-, I- and NO3-. Elemental analyses and spectral (IR, electronic studies of the synthesized complexes suggest the presence of octahedral, environment around the central metal ion. These complexes were also subjected to study their antimicrobial screening against, Gram positive bacteria Candida albicans and gram negative bacteria Escherichia coli by disc diffusion technique.

  2. Moessbauer study of iron(II) and iron(III) complexes of some nitrogen-, oxygen- and sulphur donor ligands, reduction of iron(III) by the mercaptide group

    Energy Technology Data Exchange (ETDEWEB)

    Sawhney, G.L.; Baijal, J.S. (Delhi Univ. (India). Dept. of Physics and Astrophysics); Chandra, S. (Zakir Hussain College, Ajmeri Gate, Delhi (India). Dept. of Chemistry); Pandeya, K.B. (Delhi Univ. (India). Dept. of Chemistry)


    Complex formation reactions of iron(II) and iron(III) with semicarbazones and thiosemicarbazones of pyruvic acid and phenyl pyruvic acid have been studied by magnetic measurements and Moessbauer spectroscopy. With iron(II), all the ligands form hexa-coordinated octahedral complexes of the type Fe(ligand-H/sub 2/). With iron(III) semicarbazones, complexes of the composition (Fe(ligand-H)/sub 2/)(OH) are formed. Thiosemicarbazones first reduce iron(III) to iron(II) and then form iron(II) complexes of the type Fe(ligand-H)/sub 2/.

  3. 吲哚基丁烯酮缩氨基硫脲配合物的合成及生物活性%Synthesis and biological activities of transition metal complexes with the schiff base ligand indolyi substituted 3-buten-2-one thiosemicarbazone

    Institute of Scientific and Technical Information of China (English)

    孙纲春; 曲建强; 王流芳; 陈耐生; 陈晓光; 李燕; 谢晶曦



  4. Mechanism of the induction of endoplasmic reticulum stress by the anti-cancer agent, di-2-pyridylketone 4,4-dimethyl-3-thiosemicarbazone (Dp44mT): Activation of PERK/eIF2α, IRE1α, ATF6 and calmodulin kinase. (United States)

    Merlot, Angelica M; Shafie, Nurul H; Yu, Yu; Richardson, Vera; Jansson, Patric J; Sahni, Sumit; Lane, Darius J R; Kovacevic, Zaklina; Kalinowski, Danuta S; Richardson, Des R


    The endoplasmic reticulum (ER) plays a major role in the synthesis, maturation and folding of proteins and is a critical calcium (Ca(2+)) reservoir. Cellular stresses lead to an overwhelming accumulation of misfolded proteins in the ER, leading to ER stress and the activation of the unfolded protein response (UPR). In the stressful tumor microenvironment, the UPR maintains ER homeostasis and enables tumor survival. Thus, a novel strategy for cancer therapeutics is to overcome chronically activated ER stress by triggering pro-apoptotic pathways of the UPR. Considering this, the mechanisms by which the novel anti-cancer agent, Dp44mT, can target the ER stress response pathways were investigated in multiple cell-types. Our results demonstrate that the cytotoxic chelator, Dp44mT, which forms redox-active metal complexes, significantly: (1) increased ER stress-associated pro-apoptotic signaling molecules (i.e., p-eIF2α, ATF4, CHOP); (2) increased IRE1α phosphorylation (p-IRE1α) and XBP1 mRNA splicing; (3) reduced expression of ER stress-associated cell survival signaling molecules (e.g., XBP1s and p58(IPK)); (4) increased cleavage of the transcription factor, ATF6, which enhances expression of its downstream targets (i.e., CHOP and BiP); and (5) increased phosphorylation of CaMKII that induces apoptosis. In contrast to Dp44mT, the iron chelator, DFO, which forms redox-inactive iron complexes, did not affect BiP, p-IRE1α, XBP1 or p58(IPK) levels. This study highlights the ability of a novel cancer therapeutic (i.e., Dp44mT) to target the pro-apoptotic functions of the UPR via cellular metal sequestration and redox stress. Assessment of ER stress-mediated apoptosis is fundamental to the understanding of the pharmacology of chelation for cancer treatment.

  5. A porous crystal of Ni(Ⅱ) complex with vanillic thiosemicarbazone ligands and methanol solvate assembling via hydrogen bonds%香草醛缩氨基硫脲合Ni(Ⅱ)配合物的合成及晶体结构

    Institute of Scientific and Technical Information of China (English)

    吴雪立; 刘尚远; 史学芳


    利用X-射线单晶衍射技术测定了香草醛缩氨基硫脲合镍(Ⅱ)配合物甲醇溶剂化物Ni(C9H10N3O2S)2·4CH3OH)的单晶结构.测定结果表明,该晶体属单斜晶系,C2/c空间群,晶胞参数分别为d=2.571 2(6),b=0.730 41(18),c=1.656 3(4)nm,β=104.212(4)°,V=3.015 4(13)nm3,Z=4.在晶体结构中,中心离子Ni(Ⅱ)与2个配体中的N、S原子形成四配位的平面四边形结构,配体在与Ni(Ⅱ)配位时,其结构发生硫酮式与硫醇式互变异构,最终以硫醇阴离子形式与Ni(Ⅱ)配位,因而得到中性配位单元.相邻配住单元通过N3-H3A…S1氢键形成一维链状结构;甲醇分子既作为质子的受体又作为质子的给体,每个配位单元通过多重O-H…O、N-H…O氢键形成溶剂化物,生成沿ab平面的氢键二维结构;计算表明,包结在其中的甲醇客体构成一维孔道结构,占据晶格体积的35.4%.

  6. Synthesis and Characterization of Some Multi-substituted Thiosemicarbazones as the Multi-dental Ligands of Metal Ions%新型多取代硫代半卡巴腙类配体的合成与结构表征

    Institute of Scientific and Technical Information of China (English)

    赵文献; 赵明根


    为发展金属离子配体,设计合成了一系列新型多取代氨基硫脲.烯丙基异硫氰酸酯与水合肼溶液反应,制得4-烯丙基氨基硫脲(1).1分别与联乙酰(2,3-丁二酮)、水合茚三酮、乙二醛反应,合成出联乙酰双缩(4-烯丙基氨基硫脲)(2)、茚三酮-1,3-二缩(4-烯丙基氨基硫脲)(5)、乙二醛二缩(4-烯丙基氨基硫脲)(6).联乙酰和氨基硫脲反应制备出联乙酰双缩氨基硫脲(3),环已酮与1在无水乙醇中回流反应合成出环己酮缩(4-烯丙基氨基硫脲)(4).缩合反应操作简便,条件温和,反应时间只需0.5~2 h,产物收率达到70%~87%.这些化合物均未见报道,其结构通过元素分析,IR、1H NMR和MS进行了鉴定.初步测试了它们对金属离子的配位性能,发现这些多取代氨基硫脲配体很容易与Cu2+、Co2+、Ni2+、Zn2+、Ag+、Hg2+、Hg2+2及稀土离子形成稳定的螯合物.

  7. 含硫Schiff碱型配体的合成研究--芳醛缩-4-烯丙基-3-硫代氨基脲的合成与表征%Synthetic study of Schiff base type ligands containing thiocar bamide group--synthesis and characterization of aro-matic-4-allyl-3-thiosemicarbazone

    Institute of Scientific and Technical Information of China (English)

    赵明根; 范建凤; 李志英; 刘成琪


    @@ 1合成方法 在100mL反应器中,加入1.31g(0.01mol)4-烯丙基-3-硫代氨基脲,20mL无水乙醇,加热搅拌溶解,然后加入0.01mol醛及1~2滴催化剂浓盐酸,电磁搅拌,回流反应2h,趁热将反应液转移到小烧杯中,冷却,溶剂自然挥发到一定量后有晶体析出.将所得粗品用醇-水重结晶即得纯品.

  8. Syntheses, Crystal Structures and DNA-Binding Properties of Co(Ⅲ)/Cd(Ⅱ) Complexes with Quinoline Thiosemicarbazone Ligand%喹啉缩氨基硫脲Co(Ⅲ)/Cd(Ⅱ)配合物的合成、结构和DNA结合性质

    Institute of Scientific and Technical Information of China (English)

    毛盼东; 闫玲玲; 王文静; 杨倩倩; 崔猛强; 王元; 吴伟娜


    合成并通过单晶衍射、元素分析、红外光谱表征了配合物[CoL2]Cl· 2CH3OH (1)和[CdL2](2)的结构(HL为喹啉-8-甲醛缩硫代氨基脲).单晶衍射结果表明,配合物1和2中金属离子采取相同的配位模式,分别与来自硫醇化脱质子的配体L-的4个N原子和2个S原子配位,采取扭曲的八面体配位构型.配合物1和2能够与DNA结合,结合模式分别为静电结合和部分插入.

  9. Synthesis, Crystal Structures, and Bioactivities of NiⅡ and ZnⅡ Complexes with Pyridine-3-carbaldehyde Thiosemicarbazone%吡啶-3-甲醛缩氨基硫脲合镍(Ⅱ)、锌(Ⅱ)配合物的合成、晶结构及生物活性

    Institute of Scientific and Technical Information of China (English)

    边贺东; 李春英; 梁宇宁; 郭桂全; 于青; 梁宏


    The NiⅡ and ZnⅡ complexes with pyridine-3-carbaldehyde thiosemiearbazone (HL) have been synthesized and characterized by X-ray diffraction. In the [NiL2] (1), the NiⅡ atom was four-coordinated to form a square geometry by two nitrogen atoms and two sulfur atoms from two different deprotonated ligands. In [Zn(HL)2(C2H5OH)2(H2O)2](NO3)2 (2), the ZnⅡ atom was in a distorted octahedral geometry coordinated by two neutral ligands, two ethanol molecules,and two water molecules. The binding of the two complexes with calf thymus DNA has been investigated by absorption, luminescence titrations. The results suggest that both the two complex intercalates into DNA base pairs.Antimicrobial activities of the free ligand and the two complexes against Staphylococcus Aureus, β-hemolytic streptococcus, Streptococcus Pneumoniae, Bacillus Anthracis shows that the free ligand and 1 did not inhibit the growth of the test microorganisms and 2 showed weak activities against the three former tested microorganisms.%本文合成并表征了吡啶-3-甲醛缩氨基硫脲(HL)合镍(Ⅱ)、锌(Ⅱ)配合物.在配合物[NiL2(1)中,镍(Ⅱ)离子与来自2个脱氢配体的2个氮原子和2个硫原子配位.形成四配位的平面正方形构型.在配合物[Zn(HL)2(C2H5OH)2(H2O)2](NO3)2(2)中,锌(Ⅱ)离子与2个中性配体、2个乙醇分子和2个水分子配位,配位原子在锌(Ⅱ)离子周围形成畸变的八面体构型.通过荧光吸收法研究了配合物1、2与小牛胸腺DNA的作用机理.结果表明,这2个配合物均以插入形式进入DNA的碱基对.此外,还研究了配体及2个配合物对金黄色葡萄球菌、乙型溶血性链球菌、肺炎链球菌、炭疽杆菌的抗菌活性.结果表明,配体及配合物1对上述测试菌种无抑制作用.配合物2对前面3种有弱的抑菌作用.

  10. 桦木酮缩氨基硫脲铜、银、钯、镉金属配合物的合成、表征与生物活性研究%Synthesis, characterization and biological activity of cooper(Ⅱ),silver(Ⅰ), palladium(Ⅱ) and cadmium(Ⅱ) complexes of betulone thiosemicarbazone

    Institute of Scientific and Technical Information of China (English)

    楚立彬; 王葛阳; 朴凤玉; 韩荣弼


    运用拼合原理,合成了4种桦木酮缩氨基硫脲配体及其铜、银、镉、钯金属配合物,通过核磁共振氢谱(1H NMR)、红外光谱(IR)、元素分析、热重谱(TG)、飞行时间质谱(MALDI-TOF-MS)和元素分析对配体和配合物进行了结构表征.以最小抑菌浓度(MIC)评价了S.aureus 4220、S.mutans 3289、S.mutans 3065、E.coli 1924和E.coli 1356的抑菌活性.结果表明:Ag(L4)2Cl2·2H2O对S.aureus 4220、S.mutans 3065和E.coli 1924具有相对较好的抑制作用;Ag(L1)2NO3·2MeOH、Cu(L3)2Cl2·H2O、Ag(L3)2Cl·3H2O、Cd(L3)2Cl2、Cu(L4)2Cl2和Ag(L4)2Cl2 ·2H2O对Hela细胞有显著的抑制作用.

  11. N-Methylpyridinium tosylate catalyzed green and efficient synthesis of some novel 2,4-disubstituted thiazoles and 4-thiazolidinones

    Institute of Scientific and Technical Information of China (English)

    Deepika Gautam; Poonam Gautam; R.P.Chaudhary


    A convenient solvent less cyclocondensation from thiosemicarbazone of benzofuranone and chloroacetic acid using an ionic liquid,N-methylpyridinium tosylate for obtaining novel 4-thiazolidinones in excellent yields is reported.Also,the green expedient synthesis of new 2,4-disubstituted thiazoles under grinding condition from phenacyl bromides and thiosemicarbazide derivatives in quantitative yields is reported.

  12. Structural design, synthesis and pharmacological evaluation of 4-thiazolidinones against Trypanosoma cruzi. (United States)

    de Oliveira Filho, Gevanio Bezerra; de Oliveira Cardoso, Marcos Veríssimo; Espíndola, José Wanderlan Pontes; Ferreira, Luiz Felipe Gomes Rebello; de Simone, Carlos Alberto; Ferreira, Rafaela Salgado; Coelho, Pollyanne Lacerda; Meira, Cássio Santana; Magalhaes Moreira, Diogo Rodrigo; Soares, Milena Botelho Pereira; Lima Leite, Ana Cristina


    Chagas disease is an infection caused by protozoan Trypanosoma cruzi, which affects approximately 8-10million people worldwide. Benznidazole is the only drug approved for treatment during the acute and asymptomatic chronic phases of Chagas disease; however, it has poor efficacy during the symptomatic chronic phase. Therefore, the development of new pharmaceuticals is needed. Here, we employed the bioisosterism to modify a potent antiparasitic and cruzain-inhibitor aryl thiosemicarbazone (4) into 4-thiazolidinones (7-21). Compounds (7-21) were prepared by using a straightforward synthesis and enabled good to excellent yields. As a chemical elucidation tool, X-ray diffraction of compound (10) revealed the geometry and conformation of this class compounds. The screening against cruzain showed that 4-thiazolidinones were less active than thiosemicarbazone (4). However, the antiparasitic activity in Y strain trypomastigotes and host cell cytotoxicity in J774 macrophages revealed that compounds (10 and 18-21) are stronger and more selective antiparasitic agents than thiosemicarbazone (4). Specifically, compounds (18-20), which carry a phenyl at position N3 of heterocyclic ring, were the most active ones, suggesting that this is a structural determinant for activity. In infected macrophages, compounds (18-20) reduced intracellular amastigotes, whereas Benznidazole did not. In T. cruzi-infected mice treated orally with 100mg/kg of compound (20), a decreased of parasitemia was observed. In conclusion, we demonstrated that the conversation of thiosemicarbazones into 4-thiazolidinones retains pharmacological property while enhances selectivity.

  13. Chalcogenated Schiff bases: Complexation with palladium(II) and Suzuki coupling reactions

    Indian Academy of Sciences (India)

    Pradhumn Singh; G K Rao; Mohd Salman Karim; Ajai K Singh


    Chalcogenated Schiff bases of 5-chloroisatin (L1-L3), 2-(methythio)benzaldehyde (L4), 2-acetylpyridine (L5) and benzaldehyde (L6-L7) have been synthesized. Both the carbonyl groups of 5- chloroisatin appear to be reactive (noticed for the first time) for making >C=N bond, of course one at a time only. The 1H, 13C{1H}, 77Se{1H} and 125Te{1H} NMR spectroscopy have been used to establish the coexistence of two products, which were found in the ratio 53:47 (E = S), 55:45 (E = Se) and 81:19 (E = Te). The larger amount is of the one in which C=O group away from NH is derivatized. The two products are not separable. Palladium complexes (1-4) of Schiff bases of other three aldehydes were synthesized. The ligands as well as complexes were characterized by multinuclear NMR spectroscopy. The crystal structures of [Pd(L4/L5)Cl][ClO4] (1/2) have been solved. The Pd-Se bond lengths are 2.4172(17) and 2.3675(4) Å, respectively for 1 and 2. The Pd-complexes (3-4) of L6-L7 were explored for Suzuki-Miyaura coupling and found promising as 0.006 mol % of 3 is sufficient to obtain good conversion with TON up to 1.58 × 104.

  14. Synthesis and characterization of cobalt(II), nickel(II), copper(II) and zinc(II) complexes with Schiff base derived from 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine. (United States)

    Singh, Kiran; Barwa, Manjeet Singh; Tyagi, Parikshit


    A few (1:1) and (1:2) metal complexes of cobalt(II), nickel(II), copper(II) and zinc(II) have been isolated with ligand derived from the condensation of 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine with 2-acetylpyridine (L(1)) and characterized by elemental analysis, conductivity measurements, infrared, electronic, (1)H NMR spectral data, magnetic and thermogravimetric analyses. Due to insolubility in water and most of the common organic solvents and infusibility at higher temperatures, all the complexes are thought to be polymeric in nature. A square-planar geometry was suggested for copper(II) and octahedral proposed for cobalt(II), nickel(II) and zinc(II). Some of the chemically synthesized compounds have been screened in vitro against the three Gram-positive (Staphylococcus aureus, Staphylococcus epidermidis and Bacillus subtilis) and two Gram-negative (Salmonella typhi and Escherichia coli) organisms. It is observed that the coordination of metal ion has pronounced effect on the microbial activities of the ligand. The metal complexes have higher antimicrobial effect than the free ligands.

  15. Lanthanide complexes of tritopic bis(hydrazone) ligands: single-molecule magnet behavior in a linear Dy(III)3 complex. (United States)

    Anwar, Muhammad U; Tandon, Santokh S; Dawe, Louise N; Habib, Fatemah; Murugesu, Muralee; Thompson, Laurence K


    Tritopic pyridinebis(hydrazone)-based ligands typically produce square M(9) [3 × 3] grid complexes with first-row transition-metal ions (e.g., M = Mn, Fe, Co, Cu, Zn), but with larger lanthanide ions, such coordination motifs are not produced, and instead linear trinuclear complexes appear to be a preferred option. The reaction of 2pomp [derived from pyridine-2,6-bis(hydrazone) and 2-acetylpyridine] with La(III), Gd(III), and Dy(III) salts produces helical linear trinuclear [Ln(3)(2pomp)(2)]-based complexes, where each metal ion occupies one of the three tridentate ligand pockets. Two ligands encompass the three metal ions, and internal connections between metal ions occur through μ-O(hydrazone) bridges. Coligands include benzoate, nitrate, and N,N-dimethylformamide. The linear Dy(III)(3) complex exhibits single-molecule magnet behavior, demonstrated through alternating-current susceptibility measurements. Slow thermal magnetic relaxation was detected in an external field of 1800 Oe, where quantum-tunneling effects were suppressed (U(eff) = 14 K).

  16. End-to-End Thiocyanato-Bridged Helical Chain Polymer and Dichlorido-Bridged Copper(II) Complexes with a Hydrazone Ligand: Synthesis, Characterisation by Electron Paramagnetic Resonance and Variable-Temperature Magnetic Studies, and Inhibitory Effects on Human Colorectal Carcinoma Cells. (United States)

    Das, Kuheli; Datta, Amitabha; Sinha, Chittaranjan; Huang, Jui-Hsien; Garribba, Eugenio; Hsiao, Ching-Sheng; Hsu, Chin-Lin


    The reactions of the tridentate hydrazone ligand, N'-[1-(pyridin-2-yl)ethylidene]acetohydrazide (HL), obtained by condensation of 2-acetylpyridine with acetic hyadrazide, with copper nitrate trihydrate in the presence of thiocyanate, or with CuCl2 produce two distinct coordination compounds, namely a one-dimensional helical coordination chain of [CuL(NCS)] n (1) units, and a doubly chlorido-bridged dinuclear complex [Cu2L2Cl2] (2) (where L=CH3C(O)=N-N=CCH3C5H4N). Single-crystal X-ray structural determination studies reveal that in complex 1, a deprotonated hydrazone ligand L(-) coordinates a copper(II) ion that is bridged to two neighbouring metal centres by SCN(-) anions, generating a one-dimensional helical coordination chain. In complex 2, two symmetry-related, adjacent copper(II) coordination entities are doubly chlorido-bridged, producing a dicopper entity with a Cu⋅⋅⋅Cu distance of 3.402 (1) Å. The two coordination compounds have been fully characterised by elemental analysis, spectroscopic techniques including IR, UV-vis and electron paramagnetic resonance, and variable-temperature magnetic studies. The biological effects of 1 and 2 on the viability of human colorectal carcinoma cells (COLO-205 and HT-29) were evaluated using an MTT assay, and the results indicate that these complexes induce a decrease in cell-population growth of human colorectal carcinoma cells with apoptosis.

  17. 一维单链4-吡啶甲醛缩氨基硫脲合锌(Ⅱ)配位聚合物[Zn(HL)(CH3COO)2·H2O]n的合成、晶体结构及配体的新颖配位模式%Synthesis and Crystal Structure of One-dimensional Single-chain Zn(Ⅱ) Complex Containing Pyridine-4-carbaldehyde Thiosemicarbazone and Novel Coordination Mode of Ligand

    Institute of Scientific and Technical Information of China (English)

    李明雪; 周静; 王敬平; 王子梁


    4-吡啶甲醛缩氨基硫脲(HL)与醋酸锌反应得到了标题配位聚合物[Zn(HL)(CH3 COO)2 ·H2 O]n (1). 采用元素分析、红外光谱、紫外光谱和单晶X射线衍射测试技术对其结构进行了表征. 单晶X射线衍射分析表明,在标题配位聚合物1中,Zn 2+ 离子与1个配体HL中的吡啶环上的氮原子,另外1个配体HL中的硫原子以及2个醋酸根上的氧原子配位,构成了锌离子的畸变四面体构型;每个HL分别以吡啶环上的氮原子和硫原子以头对尾的方式与2个锌离子配位,从而将锌离子依次桥联,形成了类螺旋形链结构,链间通过氢键和π-π相互作用形成三维网络结构. HL潜在的NNS三齿配位点中亚胺N没有配位,吡啶N和S采取头对尾的NS配位模式是比较新颖的.


    Institute of Scientific and Technical Information of China (English)

    Ibrahim Erol; Cemal Cifci


    A new type of methacrylate monomer, 2-(4-benzoylphenoxy)-2-oxoethyl methylacrylate (BOEMA) was synthesized. The radical homopolymerization of BOEMA was performed at 65℃ in a 1,4-dioxane solution with benzoyl peroxide as an initiator. The oxime and thiosemicarbazone derivatives of poly[2-(4-benzoylphenoxy)-2-oxoethyl methylacrylate] poly(BOEMA) were prepared with hydroxylamine hydrochloride, and thiosemicarbazone hydrochloride,respectively. The monomer and its homopolymer were characterized with Fourier transform infrared and NMR techniques.The thermal stabilities of poly(BOEMA) and its derivatives were investigated with thermogravimetric analysis and differential scanning calorimetry. The ultraviolet stability of the polymers was compared. The antibacterial and antifungal effects of the monomer and the polymer and its derivatives were also investigated on various bacteria and fungi. The activation energies of the thermal degradation of the polymers were calculated with the Ozawa and Kissinger methods.

  19. Preparation, spectroscopy, EXAFS, electrochemistry and pharmacology of new ruthenium(II) carbonyl complexes containing ferrocenylthiosemicarbazone and triphenylphosphine/arsine (United States)

    Prabhakaran, R.; Anantharaman, S.; Thilagavathi, M.; Kaveri, M. V.; Kalaivani, P.; Karvembu, R.; Dharmaraj, N.; Bertagnolli, H.; Dallemer, F.; Natarajan, K.


    A new series of new hetero-bimetallic complexes containing iron and ruthenium of the general formula [RuCl(CO)(B)(EPh 3)(L)] (where E = P or As; B = PPh 3, AsPh 3, py or pip; L = ferrocene derived monobasic bidentate thiosemicarbazone ligand) have been synthesized by the reaction between ferrocene-derived thiosemicarbazones and ruthenium(II) complexes of the type [RuHCl(CO)(B)(EPh 3) 2] (where E = P or As; B = PPh 3, AsPh 3, py or pip). The new complexes have been characterized by elemental analyses, IR, electronic, NMR ( 1H, 13C and 31P), EXAFS (extended X-ray absorption fine structure spectroscopy) and cyclic voltammetric techniques. Antibacterial activity of the new complexes has been screened against Escherichia coli, Vibrio cholerae, and Pseudomonas aeruginosa species.

  20. Crystal structure of (E-2-[4-(4-hydroxyphenylbutan-2-ylidene]hydrazine-1-carbothioamide

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    Adriano Bof de Oliveira


    Full Text Available The title compound, C11H15N3OS, is a thiosemicarbazone derivative of the raspberry ketone rheosmin [systematic name: 4-(4-hydroxyphenylbutane-2-one]. The molecule deviates from planarity, with the bridging C—C—C=N torsion angle equal to −101.3 (2°. The maximum deviation from the mean plane of the non-H atoms of the thiosemicarbazone fragment [C=N—N—C(= S—N] is 0.085 (5 Å for the Schiff base N atom, and the dihedral angle between this mean plane and the aromatic ring is 50.31 (8°. In the crystal, molecules are linked by N—H...O, N—H...S and O—H...S hydrogen bonds, forming a three-dimensional structure, with the molecules stacked along [011].

  1. Novel Steroidal (6R)-Spiro-1,3,4-thiadiazoline Derivatives as Anti-bacterial Agents

    Institute of Scientific and Technical Information of China (English)

    Khan Salman A.; Asiri, Abdullah M.


    Novel steroidal (6R)-spiro-1,3,4-thiadiazoline derivatives have been synthesized by the cyclization of steroidal thiosemiearbazones. Thiosemicarbazones have been synthesized by the reaction of steroidal ketones with thiosemi- carbazide. All the compounds have been characterized by IR, 1H NMR, mass and elemental analyses. The antibacterial activities of these compounds have been first tested in vitro by the disk diffusion assay against two Gram-positive and two Gram-negative bacteria, and then the minimum inhibitory concentration (MIC) values have been determined with the reference of standard drug amoxicillin. The results showed that steroidal thiadiazoline de- rivatives exhibited better antibacterial activity than the steroidal thiosemicarbazone derivatives. Chloro and acetoxy substituents on the 3β-position of the steroidal thiadiazoline ring increased the anti-bacterial activity. Among all the compounds, compounds 7 and 8 were found better inhibitors as compared to the respective drug amoxicillin.

  2. Characterization of A New Organic Photochromic Compound

    Institute of Scientific and Technical Information of China (English)

    LIU,Guang-Fei; LIU,Lang; JIA,Dian-Zeng; HU,Xin; YU,Kai-Bei


    @@ A new organic photochromic compound, 1-phenyl-3-methyl-4-(4-fluoro)-benzal-5-pyrazolone ethanyl-thiosemicarbazone (PM4FBP-ETSC) was found to undergo photochromic reactions in the solid state. Upon irradiation with 365nm light the white powder sample turned light yellow. The photochromic properties were characterized by the time-dependent UV-vis reflective spectra. The structure of PM4FBP-ETSC was determined by single crystal X-ray diffraction.

  3. One- and Two-photon Excited Fluorescence of Zinc(Ⅱ), Cadmium(Ⅱ) Complexes Containing Phenothiazine Ligand

    Institute of Scientific and Technical Information of China (English)


    A new ligand, 10-ethylphenothiazinyl - 3 - yl - methylene thiosemicarbazon (HL) and its complexes ML2 (M=Zn2+, Cd2+), which exhibit intensive two-photon excited (TPE) fluorescence at 800 nm laser pulses in femtosecond regime, were synthesized and characterized.The measured power dependence of the fluorescence signals provided direct evidence for TPE.All of them exhibited a large two-photon absorptive cross section and, more importantly from the application point of view, high photochemical/photothermal stability.

  4. Kinetics of Schiff base on Escherichia coli by microcalorimetry

    Institute of Scientific and Technical Information of China (English)

    许名飞; 李新海; 万洪文; 刘义


    The influence of four kinds of Schiff bases on a strain of Escherichia coli was studied by microcalorimetry. Differences in their capabilities of suppressing the metabolism of this bacterium were observed. The results show that the extent and duration of the inhibitory effect on the metabolism as judged from the multiplication rate constant, k, varies with different Schiff bases.The multiplication rate constant k, of Escherichia coli (in log phase) in the presence of Mo-salicylioaldehyde-thiadizole, Mo-piperonaldehyde-thiosemicarbazone and Mo-3-methoxy-salicylicaldehyde-thiadizole decreases with the increase of concentrations of compounds c, and the relationships between k and c, maximum heat production rate Pm and c, peak time of growth curves tp and c are of linearity. For Mo-6-nitro-pieronalde-thiosemicarbazone, the multiplication rate constant is constant irrespective of variation in concentration. The sequence of antibiotic activity of Schiff base is: Mo-salicylioaldehyde-thiadizole>Mo-3-methoxy-salicylicaldehyde-thiadizole>Mo-piperonaldehyde-thiosemicarbazone> 6-nitro-pieronalde-thiosemicarbazone.

  5. Synthesis, X-ray crystal structures, thermal and electrochemical properties of thiosemicarbazidatodioxouranium(VI) complexes. (United States)

    Sahin, Musa; Koca, Atıf; Ozdemir, Namık; Dinçer, Muharrem; Büyükgüngör, Orhan; Bal-Demirci, Tülay; Ulküseven, Bahri


    The stable uranyl complexes, [UO(2)(L)C(9)H(19)OH], were obtained from 3,5-dichlorosalicyl-(L(I)) and salicyl-aldehyde-S-propyl-thiosemicarbazones (L(II)) with substituted-salicylaldehyde in nonyl alcohol. The structures of the complexes have been characterized by elemental analysis, IR, (1)H NMR, conductivity, magnetic moment measurements, cyclic voltammetry, thermal gravimetric analysis and single crystal X-ray diffraction technique. The U(VI) centre is seven-coordinated in a distorted pentagonal bipyramidal geometry. The relative orientations of the nonyl alcohol and S-propyl group in the title complexes are completely different due to different crystal packing. Electrochemical behaviors of the thiosemicarbazone ligands and the uranyl complexes were studied using cyclic voltammetry and square wave voltammetry. Redox processes of the compounds are significantly influenced by the central metal ions and the nature of substituents on the thiosemicarbazones, which are important factors in controlling the redox properties. In situ spectroelectrochemical studies were employed to determine the colors and spectra of electro-generated species of the complexes.

  6. Synthesis and Structural Characterization of Schiff Base Ligand and their Metal Complexes

    Directory of Open Access Journals (Sweden)

    Amit Kumar Gautam


    Full Text Available In the present work, the synthesis and structural characterization of a 2-phenyl- 3(benzamido propyl quinazoline (3H -4- one semicarbazone/ thiosemicarbazone hydrochloride and its metal complexes have been reported. All the synthesized compounds were characterized by using various physico-chemical techniques such as Infrared spectra, electronic spectra, molar conductivity and magnetic susceptibility measurements. The ligand and metal ions reacted to form in the 2:1 ratio as found from the elemental analyses and general stiochiometry was determined, [M(PBPQS2X2] and [M(PBPQT2X2]; where M = Co(II, Ni(II and Cu(II; PBPQS = 2-phenyl- 3 (benzamido propyl quinazoline (3H -4- one semicarbazone and PBPQT = 2- phenyl- 3 (benzamido propyl quinazoline (3H -4- one thiosemicarbazone. On the basis of analytical data, a proposed structure for the Cu(II complexes are distorted octahedral and those for Co(II and Ni(II complexes are octahedral. Ligands PBPQS/ PBPQT have been proposed to act in a bidentate manner co-ordinating to the metal ions though azomethine nitrogen and oxygen/ sulphur atom of either semicarbazone/ thiosemicarbazone moiety. The remaining co-ordination sites are occupied by negative ions such as Cl-, Br-, I- or NO3-. The ligands and its metal complexes were tested for their possible antimicrobial potentials.

  7. Thiosemicabazone based fluorescent chemosensor for transition metal ions in aqueous medium

    Energy Technology Data Exchange (ETDEWEB)

    Udhayakumari, Duraisamy; Suganya, Sivalingam; Velmathi, Sivan, E-mail:


    Highly efficient fluorescent chemosensors for metal ions have been synthesized by using thiosemicarbazide and aromatic aldehydes. Detection of transition metal ions was performed via UV–vis and fluorescence spectroscopic methods. This is the first report on thiosemicarbazone based sensor capable of detecting transition metal ions in aqueous medium. The binding constant, stoichiometry of the complex were confirmed by using B–H plot and Job's plot method. The fluorescence enhancement of thiosemicarbazones on binding with Hg{sup 2+}, Zn{sup 2+}, Co{sup 2+}, Ni{sup 2+} and Sn{sup 2+} ions is due to the inhibition of photoinduced electron transfer mechanism whereas, quenching of fluorescence is attributed to the photoinduced electron transfer mechanism in case of Cu{sup 2+} and Mn{sup 2+} ions. -- Graphical abstract: Three highly sensitive aromatic thiosemicarbazones act as a fluorescent chemosensor for cations. Detection of transition metal ions was performed via UV–vis and fluorescence spectroscopic methods. This represents the first report on thiosemicarbazone based sensor capable of detecting transition metal ions in aqueous medium. The binding constant, stoichiometry of the complex was confirmed by using B–H plot and Job's plot method. The fluorescence enhancement of thiosemicarbazones on binding with Hg{sup 2+} , Zn{sup 2+}, Co{sup 2+}, Ni{sup 2+} and Sn{sup 2+} ions is due to the inhibition of photoinduced electron transfer whereas, in the case of Cu{sup 2+} and Mn{sup 2+} ions quenching of fluorescence occurring is attributed to the photoinduced electron transfer mechanism. Highlights: • The receptors were synthesized and studied for its optical/fluorescence emission properties. • R1+Zn{sup 2+}/Co{sup 2+}/Ni{sup 2+} and R2+Hg{sup 2+}/Sn{sup 2+} exhibits fluorescence enhancement via inhibition of PET. • R1+Cu{sup 2+} and R3+Mn{sup 2+} exhibits fluorescence quenching via PET mechanism.

  8. The Effects of Filter Ventilation on Flavor Constituents in Cigarette Smoke

    Directory of Open Access Journals (Sweden)

    Jing Y


    Full Text Available The deliveries of 20 added flavor constituents, total particulate matter (TPM, nicotine, ‘tar’ carbon monoxide and water in cigarette mainstream smoke were studied when filter ventilation was 0, 10%, 30%, 50% and 70%, respectively. The flavor substance test was done by addition of standard samples. The flavor constituents in cigarette smoke condensate were separated by simultaneous distillation-extraction (SDE and capillary gas chromatography (GC. The flavor constituents were identified and determined quantitatively by gas chromatography-mass spectrometry (GC-MS and GC. The flavors studied were methylpyrazine, furaldehyde, 5-methylfuraldehyde, benzaldehyde, 6-methyl-5-hepten-2-one, trimethylpyrazine, 2-acetylpyridine, phenylacetaldehyde, acetophenone, linalool, b-phenylethyl alcohol, isophorone, oxoisophorone, benzyl acetate, menthol, ethyl octanoate, b-damascenone, b-damascone, geranylacetone and b-ionone. The deliveries of TPM, nicotine, ‘tar’ carbon monoxide and water in mainstream smoke were determined according to International Standard methods. It was found that the flavor constituents and routine components in mainstream smoke decreased in different proportions as the filter ventilation increased. Carbon monoxide and ‘tar’ decreased more than nicotine. The flavor constituents with lower boiling points and lower molecular weights decreased more than those with higher boiling points and higher molecular weights. With the increase of filter ventilation, not only is the amount of smoke components reduced and the smoke taste weakened, but also the composition of smoke is modified and the quality of aroma changed slightly. These findings should be considered when developing low-‘tar’ cigarettes through the use of filter ventilation technology.

  9. [Hexane-2,5-dione bis(thiosemicarbazonato]nickel(II

    Directory of Open Access Journals (Sweden)

    Mohammad Safi Shalamzari


    Full Text Available In the title compound, [Ni(C8H14N6S2], the NiII ion is coordinated by N2S2 donor atoms of the tetradentate thiosemicarbazone ligand, and has a slightly distorted square-planar geometry. In the crystal, inversion-related molecules are linked via pairs of N—H...N and N—H...S hydrogen bonds, forming R22(8 ring motifs. Molecules are further linked by slightly weaker N—H...N, N—H...S and C—H...S hydrogen bonds, forming two-dimensional networks which lie parallel to the bc plane.

  10. Bis(pyridine-2-carbaldehyde thiosemicarbazonezinc(II dinitrate dihydrate

    Directory of Open Access Journals (Sweden)

    Jian-Quan Wang


    Full Text Available The asymmetric unit of the title compound, [Zn(C7H8N4S2](NO32·2H2O, contains two Zn(pht2 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.

  11. Crystal Structure and Photochromism of a Novel Organic Compound Condensed by Pyrazolone with Thiosemicarbazide

    Institute of Scientific and Technical Information of China (English)

    LIU, Guang-Fei; LIU, Lang; JlA, Dian-Zeng; ZHANG, Li


    A new photochromic organic compound of thiosemicarbazone, 4-(p-bromo-α-methylaminothiocarbonyl hydrazonobenzal)-2,5-dihydro-3-methyl-5-oxo-l-phenyl pyrazole, was synthesized and characterized by elemental analyses, IR, 1H NMR spectra, and X-ray single-crystal diffraction analysis. The compound exhibited an interesting photochromism in the solid state when irradiated by ultraviolet light at 365 nm. The photochromic kinetics was studied by the time-dependent powder UV-Vis reflectance spectra. The intermolecular and intramolecular hydrogen-bonding interactions may be responsible for the photochromic phenomenon.

  12. Crystal structure of dimethyl 2-((2Z,5Z)-5-(2-meth-oxy-2-oxo-ethyl-idene)-2-{(E)-[2-methyl-5-(prop-1-en-2-yl)cyclo-hex-2-enyl-idene]hydrazinyl-idene}-4-oxo-thia-zolidin-3-yl)fumarate. (United States)

    N'ait Ousidi, Abdellah; Ait Itto, My Youssef; Auhmani, Aziz; Riahi, Abdelkhalek; Auhmani, Abdelwahed; Daran, Jean-Claude


    The crystal structure and the conformation of the title compound, C22H27N3O7S, were determined from the synthetic pathway and by X-ray analysis. This compound is a new 4-thia-zolidinone derivative prepared and isolated as pure product from thio-semicarbazone carvone. The mol-ecule is built up from an oxo-thia-zolidine ring tetra-substituted by a meth-oxy-oxo-ethyl-idene, a maleate, an oxygen and a cyclo-hexyl-idene-hydrazone. The cyclo-hexyl-idene ring is statistically disordered over two positions, resulting in an inversion of configuration for the substituted carbon.

  13. Synthesis, Structure and Antibacterial Activities of 4-BBTS Schiff Base and Its Complexes

    Institute of Scientific and Technical Information of China (English)

    LI Pei-Fan; LIU Bin; WANG Jin-Ling


    4-Bromobenzaldehyde thiosemicarbazone Schiff base (4-BBTS) and its Cu(Ⅱ),Zn(Ⅱ), Co(Ⅱ) and Ni(Ⅱ) complexes were synthesized and characterized by elemental analysis, UV,IR, MS, 1H NMR, and molar conductivity. Using disc diffusion method, the antibacterial activity tests were conducted. The results revealed that the ligand as well as all the complexes exhibits good antibacterial activities against E. Coli. and S. Aureus. Moreover, Cu(Ⅱ) complex shows the best antibacterial activity, which provides beneficial reference for studying the relationship between the structures and performances.


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    Full Text Available The azomethines have broad applications in food and dyestuff industries, and in analytical chemistry, catalysis and also in the field of agrochemical. These have played an influential part in the improvement of modern coordination chemistry, but also they can also be found at key points in the development of inorganic biochemistry, catalysis and also in optical materials. The present paper describes coloring properties of wool fabric colored by new dyestuffs - azomethines, derivate of isatin. Synthesizing of dyestuffs can often have one to six chromogen, which can be defined as the photoactive components that contain colored or uncolored absorbent components. In addition of monoazo, diazo, poly-azo, anthraquinone, xanthan and similar systems, the azomethines or imines, also includes to the chromogen groups. Azomethines, such as, isatin-3-hydrazone, isatin-3-thiosemicarbazone and isatin-3-phenylhydrazone, were synthesized and their coloring performance on wool fabric assessed. The synthesized azomethines showed very good substantively for wool fibers with good coloring performance according to CIEL*a*b* system which characterized quantitative and qualitative coloring property. Dyestuff 3 or isatin-3-phenylhydrazone bound to woolen textiles to a greater extent and greater intensity (minimum value of L. Dyestuff 2 or isatin-3-thiosemicarbazone linked to the minimum amount for textiles (the largest value of L. Although it must be noted that it is a lighter shade (yellow color as opposed to the dyestuff 3 (red color.

  15. Preparation of zinc sulfide nanocrystallites from single-molecule precursors (United States)

    Palve, Anil M.; Garje, Shivram S.


    Zinc sulfide nanocrystallites were prepared using Zinc(II) thiosemicarbazone complexes of the types Zn(L) 2 and ZnCl 2(LH) 2 (where, LH=thiosemicarbazones of cinnamaldehyde, 4-chlorobenzaldehyde, indol-3-carboxaldehyde and thiophene-2-carboxaldehyde) as single source precursors by solvothermal decomposition in ethylene glycol and ethylene diamine in few cases. The materials were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction, energy dispersive X-ray analysis and UV-vis and IR spectroscopy. Solvothermal decomposition in ethylene glycol resulted in the formation of hexagonal ZnS (JCPDS: 36-1450) as evident from the XRD patterns. However, XRD shows formation of hybrid material, ZnS 0.5EN in case of solvothermal decomposition in ethylenediamine. Infrared spectra authenticate the capping of ethylene glycol and ethylenediamine on ZnS and ZnS 0.5EN, respectively. TEM images showed formation of spherical nanoparticles for the materials obtained from ethylene glycol, whereas plate-like morphology is observed in case of materials obtained from ethylene diamine. The blue shift of absorption bands compared to bands of bulk materials in the UV-vis spectra supports the formation of smaller particles.

  16. Some technetium complexes for labelling red blood cells

    Energy Technology Data Exchange (ETDEWEB)

    Emery, M.F.


    A new approach to produce technetium labelled red blood cells, used routinely in diagnostic nuclear medicine, is reported. The enzyme Carbonic Anhydrase (CA), present in erythrocytes, is strongly inhibited by primary aromatic sulphonamides, which bind at the enzyme active site. Three types of ligand able to coordinate to technetium and suitable for modification to include a primary aromatic sulphonamide group were studied; bis(thiosemicarbazones), Schiff bases and some propylene amine oximes. The experimental conditions needed to label the ligands were determined. Both the thiosemicarbazone and propyleneamine oxime derivatives were labelled, but under no conditions attempted were the Schiff bases complexed by Technetium. The two major isozymes of Human Carbonic Anhydrase, HCA I and HCA II, were isolated from blood. The strength of binding of the free ligands SET, PN130 and PN135 with each of the isozymes was measured and expressed as the Dissociation Constant K{sub d}. The rate of uptake of the technetium complexes into washed RBCs and whole blood was measured and found to be much slower in whole blood. The biodistribution of both TcPN130 and TcPN135 in rats was determined and scintigraphic images for the TcPN130 complex were recorded. Attempts to synthesise the Tc-99 analogues on the milligram scale to allow chemical characterisation of these complexes were unsuccessful. (author).

  17. Beyond Metal-Hydrides: Non-Transition-Metal and Metal-Free Ligand-Centered Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation. (United States)

    Haddad, Andrew Z; Garabato, Brady D; Kozlowski, Pawel M; Buchanan, Robert M; Grapperhaus, Craig A


    A new pathway for homogeneous electrocatalytic H2 evolution and H2 oxidation has been developed using a redox active thiosemicarbazone and its zinc complex as seminal metal-free and transition-metal-free examples. Diacetyl-bis(N-4-methyl-3-thiosemicarbazone) and zinc diacetyl-bis(N-4-methyl-3-thiosemicarbazide) display the highest reported TOFs of any homogeneous ligand-centered H2 evolution catalyst, 1320 and 1170 s(-1), respectively, while the zinc complex also displays one of the highest reported TOF values for H2 oxidation, 72 s(-1), of any homogeneous catalyst. Catalysis proceeds via ligand-centered proton-transfer and electron-transfer events while avoiding traditional metal-hydride intermediates. The unique mechanism is consistent with electrochemical results and is further supported by density functional theory. The results identify a new direction for the design of electrocatalysts for H2 evolution and H2 oxidation that are not reliant on metal-hydride intermediates.

  18. Potent 5-nitrofuran derivatives inhibitors of Trypanosoma cruzi growth: Electrochemical, spectroscopic and biological studies (United States)

    Maria Aravena, C.; Claudio Olea, A.; Cerecetto, Hugo; González, Mercedes; Maya, Juan Diego; Rodríguez-Becerra, Jorge


    Cyclic voltammetry and electron spin resonance techniques were used in the investigation of several potential antiprotozoal containing thiosemicarbazone and carbamate nitrofurans. In the electrochemical behaviour, a self-protonation process involving the nitro group was observed. The reactivity of the nitro anion radical for these derivatives with glutathione, a biological relevant thiol, was also studied in means of cyclic voltammetry. These studies demonstrated that glutathione could react with radical species from 5-nitrofuryl system. Furthermore, from the voltammetric results, some parameters of biological significance as E71 (indicative of the biological nitro anion radical formation), and K (thermodynamic indicator the of oxygen redox cycling) have been calculated. We also evaluated the stability of the nitro anion radical in terms of the dimerization constant ( kd). The nitrofuran-free radicals from cyclic voltammetry were characterized by electron spin resonance. A clear dependence between both the thiosemicarbazone or carbamate substructure and the length of the linker, furyl- or furylpropenyl-spacer, and the delocalization of the unpaired electron was observed. Through of biological assays we obtained important parameters that account for the selective anti-trypanosomal activity of these derivatives. The trypomastigote viability study showed that all derivatives are as active as in the epimastigote form of the parasite in a doses dependent manner.

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

    John, E K; Green, M A


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

  20. Synthesis, crystal structure, DNA interaction and antioxidant activities of two novel water-soluble Cu2+ complexes derivated from 2-oxo-quinoline-3-carbaldehyde Schiff-bases. (United States)

    Liu, Zeng-Chen; Wang, Bao-Dui; Yang, Zheng-Yin; Li, Yong; Qin, Dong-Dong; Li, Tian-Rong


    Two novel 2-oxo-quinoline-3-carbaldehyde (4'-hydroxybenzoyl) hydrazone, thiosemicarbazone ligands and its corresponding Cu(2+) complexes were synthesized, and the two complexes' structures were determined by X-ray single crystal diffraction. The interaction of the two Cu(2+) complexes with calf thymus DNA (CT-DNA) was investigated by electronic absorption spectroscopy, fluorescence spectroscopy and viscosity measurement. The experimental evidences indicated that the two water-soluble Cu(2+) complexes could strongly bind to CT-DNA via an intercalation mechanism. The intrinsic binding constants of complexes 1 and 2 with CT-DNA were 7.31 x 10(6) and 2.33 x 10(6)M(-1), respectively. Furthermore, the antioxidant activities (hydroxyl radical and superoxide) of the two water-soluble metal complexes were determined by hydroxyl radical and superoxide scavenging method in vitro.

  1. Antimicrobial activity, synergism and inhibition of germ tube formation by Crocus sativus-derived compounds against Candida spp. (United States)

    Carradori, Simone; Chimenti, Paola; Fazzari, Marina; Granese, Arianna; Angiolella, Letizia


    The limited arsenal of synthetic antifungal agents and the emergence of resistant Candida strains have prompted the researchers towards the investigation of naturally occurring compounds or their semisynthetic derivatives in order to propose new innovative hit compounds or new antifungal combinations endowed with reduced toxicity. We explored the anti-Candida effects, for the first time, of two bioactive compounds from Crocus sativus stigmas, namely crocin 1 and safranal, and some semisynthetic derivatives of safranal obtaining promising biological results in terms of minimum inhibitory concentration/minimum fungicidal concentration (MIC/MFC) values, synergism and reduction in the germ tube formation. Safranal and its thiosemicarbazone derivative 5 were shown to display good activity against Candida spp.

  2. Synthesis of New Schiff Bases Containing Thiophene Moiety

    Institute of Scientific and Technical Information of China (English)

    ZhuWan-ren; HuPei-zhi; LiMei-ying; HuangXiao-ling; WuCheng-tai


    Seven new Schiff bases, which are 4,4,4-trifluoro-1- ( 2-thienyl )- 1-butanone-3-Z, Z =-thiosemicarbazone (a) ;-thiocarbohydrazone ( b),-benzoic hydrazone (e), -( o-hydroxyphenyl) imine (d) ,-nicotinic hydrazone (e) ,-salicylic hydrazone ( f), and -(p-fluoro-m-chlorophenyl) imine (g),have been synthesized by reaction of 4, 4, 4-trifluoro-l-(2-thienyl)-l, 3-butanedione (TFTBD) with corresponding hydrazides or anilines, acetic acid or p-toluence sulfonic acid as catalyst, and characterized by Elemental analysis, IR, UV-Vis,1H NMR and MS. The MS spectra confirmed that the —C3=O condensed with primary amino group. Tautomerism of the compounds is discussed.

  3. Synthesis and in vitro Evaluation of New Benzothiazole Derivatives as Schistosomicidal Agents

    Directory of Open Access Journals (Sweden)

    Mona A Mahran


    Full Text Available A series of benzothiazol-2-yl-dithiocarbamates 3a-d along with their copper complexes 4a-c were synthesized via the reaction of suitable alkyl, aralkyl or heteroaryl halides with the sodium salt of benzothiazol-2-yl-dithiocarbamic acid, followed by complexation with copper sulphate. N-(4-Acetyl-5-aryl-4,5-dihydro-1,3,4-thiadiazol-2-yl-N-benzothiazol-2-yl-acetamides 7a-c were synthesized by cyclization of the appropriate thiosemicarbazones 6a-c in acetic anhydride. Selected compounds were screened for in vitro schistosomicidal activity against Schistosoma mansoni at three different dosage levels (10, 50 and 100 μg/ mL. Three of these products, 4a-c, showed schistosomicidal activity similar to praziquantel, with 100% worm mortality at 10 μg/mL. These compounds would constitute a new class of potent schistosomicidal agents.

  4. In vitro susceptibility of sea lion poxvirus to cidofovir. (United States)

    Nollens, Hendrik H; Gulland, Frances M D; Jacobson, Elliott R; Hernandez, Jorge A; Klein, Paul A; Walsh, Michael T; Condit, Richard C


    Parapoxviruses of seals and sea lions are commonly encountered pathogens with zoonotic potential. The antiviral activity of the antiviral compounds isatin-beta-thiosemicarbazone, rifampicin, acyclovir, cidofovir and phosphonoacetic acid against a parapoxvirus (SLPV-1) isolated from a Californian sea lions (Zalophus californianus) was evaluated. Cidofovir was able to reduce virus-induced cytopathic effect of SLPV-1 in confluent monolayers when used in concentrations greater than 2microg/ml. A decreasing virus yield was observed in the presence of increasing concentrations of cidofovir, which confirmed the ability of cidofovir to inhibit SLPV-1 replication. The in vitro efficacy of cidofovir against SLPV-1 indicates the therapeutic potential of cidofovir for the treatment of infections of humans and pinnipeds with parapoxviruses of seals and sea lions. This study confirms the previously proposed therapeutic potential of cidofovir for the treatment of parapoxvirus infections.

  5. Historical Perspectives in the Development of Antiviral Agents Against Poxviruses

    Directory of Open Access Journals (Sweden)

    Erik De Clercq


    Full Text Available The poxvirus vaccinia virus (VV served as the model virus for which the first antivirals, the thiosemicarbazones, were identified. This dates back to 1950; and, although there is at present no single antiviral drug specifically licensed for the chemotherapy or -prophylaxis of poxvirus infections, numerous candidate compounds have been described over the past 50 years. These compounds include interferon and inducers thereof (i.e., polyacrylic acid, 5-substituted 2’-deoxyuridines (i.e., idoxuridine, IMP dehydrogenase inhibitors, S-adenosylhomocysteine hydrolase inhibitors, acyclic nucleoside phosphonates (such as cidofovir and alkoxyalkyl prodrugs thereof (such as CMX001, viral egress inhibitors (such as tecovirimat, and cellular kinase inhibitors (such as imatinib.

  6. DNA Binding and Cleavage Activity of Binuclear Metal Complexes with Benzil-α-Monoxime Thiosemicarbzone

    Directory of Open Access Journals (Sweden)

    M. S. Surendra Babu


    Full Text Available Transition metal complexes of copper(II, nickel(II, cobalt(II and iron(II with benzil-α-monoxime thiosemicarbazone (BMOT have been synthesized and characterized by molar conductance, magnetic moments, IR, electronic and ESR spectroscopy. Electrochemical behaviors of these complexes were investigated by cyclic voltammetric studies. The nuclease activity of these complexes has been investigated on double-stranded pBR322 circular plasmid DNA by using the gel electrophoresis experiments in presence and absence of oxidant (H2O2. In the absence of oxidant DNA cleavage by hydrolytically was observed a less discernable, whereas in presence of oxidant (H2O2 all complexes showed increased nuclease activity.

  7. Flow Injection Analysis of Mercury Using 4-(Dimethylamino Benzaldehyde-4-Ethylthiosemicarbazone as the Ionophore of a Coated Wire Electrode

    Directory of Open Access Journals (Sweden)

    Sulaiman Ab Ghani


    Full Text Available A flow injection analysis (FIA incorporating a thiosemicarbazone-based coated wire electrode (CWE was developed method for the determination of mercury(II. A 0.1 M KNO3 carrier stream with pH between 1 and 5 and flow rate of 1 mL·min−1 were used as optimum parameters. A linear plot within the concentration range of 5 × 10−6–0.1 M Hg(II, slope of 27.8 ± 1 mV per decade and correlation coefficient (R2 of 0.984 were obtained. The system was successfully applied for the determination of mercury(II in dental amalgam solutions and spiked environmental water samples. Highly reproducible measurements with relative standard deviation (RSD < 1% (n = 3 were obtained, giving a typical throughput of 30 samples·h−1.

  8. The role of coordination chemistry in the development of copper and rhenium radiopharmaceuticals. (United States)

    Donnelly, Paul S


    There are several isotopes of copper and rhenium that are of interest in the development of new molecular imaging or radiotherapeutic agents. This perspective article highlights the role of coordination chemistry in the design of copper and rhenium radiopharmaceuticals engineered to selectively target tissue of interest such as cancer cells or pathological features associated with Alzheimer's disease. The coordination chemistry of copper bis(thiosemicarbazone) derivatives and copper macrocyclic complexes is discussed in terms of their potential application as targeted positron emission tomography tracers for non-invasive diagnostic imaging. A range of rhenium complexes with different ligands with rhenium in different oxidation states are introduced and their potential to be translated to new radiotherapeutic agents discussed.

  9. New Supramolecular Complex Assembled through Hydrogen Bonds.Crystal Structure of Co(PMBP-tsc)2·2DMF·2H2O

    Institute of Scientific and Technical Information of China (English)

    UU,Lang(刘浪); JIA,Dian-Zeng(贾殿赠); QIAO,Yong-Min(乔永民); YU,Kai-Bei(郁开北)


    The structure of the complex [Co(PMBP-tsc)2.2DMF@2H2O]( PMBP-tsc= 1-phenyl-3-methyl-4-benzoylpyrazol-5-one-thiosemicarbazone) has been determined by X-ray crystallography. It crystallizes in the orthorhombic system, space group Pna21, with lattice parameters a=2.1170(3) nm, b =1.2780(10) nm, c = 1.8956(2) nm, V= 4.5258(9) nm3 and Z=4. The structure shows that Co2+ in the complex is hexacoordinated with a distorted octahedral coordination sphere.The water molecules bridge the adjacent stacks through hydrogen bonds and lead to supramolecular formation with three-dimensional network structure.

  10. Crystal structure of chlorido(2-{[2-(phenylcarbamothioylhydrazin-1-ylidene](pyridin-2-ylmethyl}pyridin-1-iumgold(I chloride sesquihydrate

    Directory of Open Access Journals (Sweden)

    Claudia C. Gatto


    Full Text Available The title complex, [AuCl(C18H16N5S]Cl·1.5H2O, may be considered as a gold(I compound with the corresponding metal site coordinated by a thiosemicarbazone ligand through the S atom. The ligand adopts an E conformation and the gold(I atom displays the expected linear geometry with a Cl atom also bonded to the metal ion [Cl—Au—S = 174.23 (5°]. One of the pyridyl rings is protonated, giving the gold complex an overall positive charge. Two solvent water molecules, one of which is located on a twofold rotation axis, and a non-coordinating chloride ion complete the structural assembly. The molecular structure is stabilized by intramolecular and intermolecular N—H...Cl, N—H...N, O—H...Cl and O—H...O hydrogen bonding.

  11. A facile synthesis of ZnS nanocrystallites by pyrolysis of single molecule precursors, Zn (cinnamtscz)2 and ZnCl2 (cinnamtsczH)2

    Indian Academy of Sciences (India)

    Anil M Palve; Shivram S Garje


    ZnS nanocrystallites were synthesised by pyrolysis method using Zn (cinnamtscz)2 and ZnCl2 (cinnamtsczH)2 (cinnamtsczH = cinnamaldehyde thiosemicarbazone) as single source precursors. The prepared ZnS nanocrystallites were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction, UV-Vis and fluorescence spectroscopy. The peak broadening in XRD and emission at shorter wavelength in fluorescence spectra showed the presence of nanocrystallites. The blue shift in UV-Vis absorption spectroscopy also proved the formation of nanocrystallites. TEM images show presence of plate-like and spherical ZnS nanoparticles obtained from Zn(cinnamtscz)2 and ZnCl2 (cinnamtsczH)2 respectively.

  12. Nickel(II) complexes containing ONS donor ligands: Synthesis, characterization, crystal structure and catalytic application towards C-C cross-coupling reactions

    Indian Academy of Sciences (India)

    Panneerselvam Anitha; Rajendran Manikandan; Paranthaman Vijayan; Govindan Prakash; Periasamy Viswanathamurthi; Ray Jay Butcher


    Nickel(II) complexes containing thiosemicarbazone ligands [Ni(L)2] (1-3) (L = 9,10-phenanthrenequinonethiosemicarbazone (HL1), 9,10-phenanthrenequinone-N-methylthio semicarbazone (HL2) and 9, 10-phenanthrenequinone-N-phenylthiosemicarbazone (HL3)) have been synthesized and characterized by elemental analysis and spectroscopic (IR, UV-Vis, 1H, 13C-NMR and ESI mass) methods. The molecular structures of complexes 1 and 2 were identified by means of single-crystal X-ray diffraction analysis. The analysis revealed that the complexes possess a distorted octahedral geometry with the ligand coordinating in a uni-negative tridentate ONS fashion. The catalytic activity of complexes towards some C–C coupling reactions (viz., Kumada-Corriu, Suzuki-Miyaura and Sonogashira) has been examined. The complexes behave as efficient catalysts in the Kumada-Corriu and Sonogashira coupling reactions rather than Suzuki-Miyaura coupling.

  13. Synthesis, Structure and Properties of Two Photochromic Compounds Containing A Pyrazolone-ring

    Institute of Scientific and Technical Information of China (English)


    Two photochromic compounds with the pyrazolone-ring as the photochromic functional structure, 2-(1'-phenyl-3'-methyl-4'-benzoformyl-pyrazolone-5')-thiosemicarbazone(PMBP-TSC) and 2-(1'-phenyl-3'-methyl-4'-benzoformyl-pyrazolone-5')-S-methylthiosemicarbazone(PMBP-MTSC), were synthesized and characterized by elemental analysis, MS, IR spectra, NMR spectra. The crystal structure of the photocolored product of PMBP-TSC was determined by single crystal XRD analysis. The results show that the photochromic phenomenon is due to the photoisomerization from enol form to keto form. Their photochromic properties were studied by powder-UV reflectance spectra under the irradiation of 200-380 nm light. The first-order rate constants of the photocoloring reaction were found to be 7.80×10-3 s-1 for compound 1A and 1.03×10-3 s-1 for compound 2A.

  14. Potentiating the cellular targeting and anti-tumor activity of Dp44mT via binding to human serum albumin: two saturable mechanisms of Dp44mT uptake by cells. (United States)

    Merlot, Angelica M; Sahni, Sumit; Lane, Darius J R; Fordham, Ashleigh M; Pantarat, Namfon; Hibbs, David E; Richardson, Vera; Doddareddy, Munikumar R; Ong, Jennifer A; Huang, Michael L H; Richardson, Des R; Kalinowski, Danuta S


    Di-2-pyridylketone 4,4-dimethyl-3-thiosemicarbazone (Dp44mT) demonstrates potent anti-cancer activity. We previously demonstrated that 14C-Dp44mT enters and targets cells through a carrier/receptor-mediated uptake process. Despite structural similarity, 2-benzoylpyridine 4-ethyl-3-thiosemicarbazone (Bp4eT) and pyridoxal isonicotinoyl hydrazone (PIH) enter cells via passive diffusion. Considering albumin alters the uptake of many drugs, we examined the effect of human serum albumin (HSA) on the cellular uptake of Dp44mT, Bp4eT and PIH. Chelator-HSA binding studies demonstrated the following order of relative affinity: Bp4eT≈PIH>Dp44mT. Interestingly, HSA decreased Bp4eT and PIH uptake, potentially due to its high affinity for the ligands. In contrast, HSA markedly stimulated Dp44mT uptake by cells, with two saturable uptake mechanisms identified. The first mechanism saturated at 5-10 µM (B(max):1.20±0.04 × 10⁷ molecules/cell; K(d):33±3 µM) and was consistent with a previously identified Dp44mT receptor/carrier. The second mechanism was of lower affinity, but higher capacity (B(max):2.90±0.12 × 10⁷ molecules/cell; K(d):65±6 µM), becoming saturated at 100 µM and was only evident in the presence of HSA. This second saturable Dp44mT uptake process was inhibited by excess HSA and had characteristics suggesting it was mediated by a specific binding site. Significantly, the HSA-mediated increase in the targeting of Dp44mT to cancer cells potentiated apoptosis and could be important for enhancing efficacy.

  15. Water-soluble ruthenium complexes bearing activity against protozoan parasites. (United States)

    Sarniguet, Cynthia; Toloza, Jeannette; Cipriani, Micaella; Lapier, Michel; Vieites, Marisol; Toledano-Magaña, Yanis; García-Ramos, Juan Carlos; Ruiz-Azuara, Lena; Moreno, Virtudes; Maya, Juan Diego; Azar, Claudio Olea; Gambino, Dinorah; Otero, Lucía


    Parasitic illnesses are major causes of human disease and misery worldwide. Among them, both amebiasis and Chagas disease, caused by the protozoan parasites, Entamoeba histolytica and Trypanosoma cruzi, are responsible for thousands of annual deaths. The lack of safe and effective chemotherapy and/or the appearance of current drug resistance make the development of novel pharmacological tools for their treatment relevant. In this sense, within the framework of the medicinal inorganic chemistry, metal-based drugs appear to be a good alternative to find a pharmacological answer to parasitic diseases. In this work, novel ruthenium complexes [RuCl2(HL)(HPTA)2]Cl2 with HL=bioactive 5-nitrofuryl containing thiosemicarbazones and PTA=1,3,5-triaza-7-phosphaadamantane have been synthesized and fully characterized. PTA was included as co-ligand in order to modulate complexes aqueous solubility. In fact, obtained complexes were water soluble. Their activity against T. cruzi and E. histolytica was evaluated in vitro. [RuCl2(HL4)(HPTA)2]Cl2 complex, with HL4=N-phenyl-5-nitrofuryl-thiosemicarbazone, was the most active compound against both parasites. In particular, it showed an excellent activity against E. histolytica (half maximal inhibitory concentration (IC50)=5.2 μM), even higher than that of the reference drug metronidazole. In addition, this complex turns out to be selective for E. histolytica (selectivity index (SI)>38). The potential mechanism of antiparasitic action of the obtained ruthenium complexes could involve oxidative stress for both parasites. Additionally, complexes could interact with DNA as second potential target by an intercalative-like mode. Obtained results could be considered a contribution in the search for metal compounds that could be active against multiple parasites.

  16. Inhibition of Chikungunya Virus Replication by 1-[(2-Methylbenzimidazol-1-yl) Methyl]-2-Oxo-Indolin-3-ylidene] Amino] Thiourea(MBZM-N-IBT). (United States)

    Mishra, Priyadarsee; Kumar, Abhishek; Mamidi, Prabhudutta; Kumar, Sameer; Basantray, Itishree; Saswat, Tanuja; Das, Indrani; Nayak, Tapas Kumar; Chattopadhyay, Subhasis; Subudhi, Bharat Bhusan; Chattopadhyay, Soma


    Chikungunya virus (CHIKV) infection is one of the most challenging human Arboviral infections with global significance and without any specific antiviral. In this investigation, 1-[(2-methylbenzimidazol-1-yl) methyl]-2-oxo-indolin-3-ylidene] amino] thiourea (MBZM-N-IBT) was synthesised as a molecular hybrid of 2-methyl benzimidazole and isatin-β-thiosemicarbazone and its anti-CHIKV property was evaluated. The release of infectious virus particles was calculated by plaque assay, expression profile of viral RNA was estimated by RT-PCR and viral protein profiles were assessed by Western blot and FACS analyses. The safety index of MBZM-N-IBT was found to be >21. The CHIKV infectious viral particle formation was abrogated around 76.02% by MBZM-N-IBT during infection in mammalian system and the viral RNA synthesis was reduced by 65.53% and 23.71% for nsP2 and E1 respectively. Surprisingly, the viral protein levels were reduced by 97% for both nsP2 and E2. In the time-of-addition experiment it abrogated viral infection at early as well as late phase of viral life cycle, which indicates about multiple mechanisms for its anti-CHIKV action. In silico analysis justified development of MBZM-N-IBT with good affinities for potential target proteins of CHIKV and related virus. With predictions of good drug-likeness property, it shows potential of a drug candidate which needs further experimental validation.

  17. Crystal structure of cis-bis-{4-phenyl-1-[(3R)-1,7,7-tri-methyl-2-oxobi-cyclo-[2.2.1]heptan-3-ylidene]thio-semicarbazidato-κ(3) O,N (1),S}cadmium(II) with an unknown solvent mol-ecule. (United States)

    Nogueira, Vanessa Senna; Bresolin, Leandro; Näther, Christian; Jess, Inke; de Oliveira, Adriano Bof


    The reaction between the racemic mixture of the camphor-4-phenyl-thio-semicarbazone derivative and cadmium acetate dihydrate yielded the title compound, [Cd(C17H20N3OS)2]. The Cd(II) ion is six-coordinated in a distorted octa-hedral environment by two deprotonated thio-semicarbazone ligands acting as an O,N,S-donor in a tridentate chelating mode, forming five-membered chelate rings. In the crystal, the mol-ecules are connected via pairs of N-H⋯S and C-H⋯S inter-actions, building centrosymmetric dimers. One of the ligands is disordered in the campher unit over two sets of sites with site-occupancy factors of 0.7 and 0.3. The structure contains additional solvent mol-ecules, which are disordered and for which no reasonable split model was found. Therefore, the data were corrected for disordered solvent using the SQUEEZE routine [Spek (2015 ▸). Acta Cryst. C71, 9-18] in PLATON. Since the disordered solvents were removed by data processing, and the number of solvent entities was a suggestion only, they were not considered in the chemical formula and subsequent chemical or crystal information.

  18. Application of Cloud Point Extraction for Cadmium in Biological Samples of Occupationally Exposed Workers: Relation Between Cadmium Exposure and Renal Lesion. (United States)

    Mortada, Wael I; Hassanien, Mohamed M; Donia, Ahmed F; Shokeir, Ahmed A


    Cadmium (Cd) level in blood and urine of soldering iron workers (n=49) and 41 matched healthy controls has been assessed. Cloud point extraction was employed for preconcentration of Cd. The Cd ions formed hydrophobic complex with 9,10-phenanthraquinone monoethyl thiosemicarbazone that was extracted by surfactant-rich phases in the nonionic surfactant Triton X-114. The surfactant-rich phase was diluted with 1 M HNO3 in methanol prior to its analysis by graphite furnace atomic absorption spectrometry. The parameters affecting the extraction efficiency of the proposed method, such as solution pH, amount of complexing agent, surfactant concentration, temperature, and incubation time, were optimized. Under the optimum experimental conditions, the detection limit and the enrichment factor were 0.04 μg L(-1) and 61, respectively. Relative standard deviation of 10 μg L(-1) Cd was less than 3.0%. The accuracy of the method was examined by analysis of certified reference materials. It was observed that soldering iron workers are liable to Cd overload as indicated by higher levels of Cd in blood and urine when compared with the controls. This exposure may lead to kidney damage indicated by elevation of urinary excretion of both N-acetyl-β-D-glucosaminidase and β2-microglobulin.

  19. Simultaneous preconcentration of copper and mercury in water samples by cloud point extraction and their determination by inductively coupled plasma atomic emission spectrometry (United States)

    Shoaee, Hamta; Roshdi, Mina; Khanlarzadeh, Nasibeh; Beiraghi, Asadollah


    A cloud-point extraction process coupled to ICP-OES by using 3-nitro benzaldehyde thiosemicarbazone (3-NBT) as complexing agent was developed for the simultaneous preconcentration and determination of copper and mercury in water samples. The variables affecting the complexation and extraction steps were optimized. Under the optimum conditions (i.e. 1.5 × 10-5 mol L-1 ligand, 0.3% (v/v) Triton X-114, 55 °C equilibrium temperature, incubation time of 30 min) the calibration graphs were linear in the range of 5-120 and 10-100 ng mL-1 with enhancement factor of 82.7 and 51.3 for Cu2+ and Hg2+, respectively. The preconcentration factors were 28.6 in both cases and detection limits were obtained 0.48 for Cu and 1.1 ng mL-1 for Hg. The precisions (R.S.D.%) for five replicate determinations at 50 ng mL-1 of copper and mercury were better than 1.8% and 3.2%, respectively. The accuracy of the proposed method is validated by analyzing a certified reference material of water (RTC-QCI-049) with satisfactory results. Finally, the proposed method was utilized successfully for the determination of copper and mercury in surface water (river), tap water and bottled mineral water samples.

  20. Crystal structures of (E-4-[1-(2-carbamothioylhydrazinylideneethyl]phenyl acetate and (E-4-[1-(2-carbamothioylhydrazinylideneethyl]phenyl benzoate

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    Vijayan Viswanathan


    Full Text Available In the title compounds, C11H13N3O2S, (I, and C16H15N3O2S, (II, the thiosemicarbazone group adopts an extended conformation. The acetate ester (I crystallizes with two independent molecules in the asymmetric unit. In the benzoate ester (II, the planes of the two aryl rings are inclined to one another by 46.70 (7°. In both compounds, there is a short intramolecular N—H...N contact present, forming an S(5 ring motif. In the crystals of both compounds, molecules are linked via pairs of N—H...S hydrogen bonds, forming dimers with R22(8 ring motifs. The dimers are linked by N—H...S and N—H...O hydrogen bonds, forming slabs parallel to (01-1. In (I, there are N—H...π and C—H...π interactions present within the slabs, while in (II, there are only N—H...π interactions present.

  1. Reaction of the Anticancer Organometallic Ruthenium Compound, [(η6-p-CymeneRu(ATSCCl]PF6 with Human Serum Albumin

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    Floyd A. Beckford


    Full Text Available The reaction of [(η6-p-cymeneRu(ATSCCl]PF6 (ATSC =9-anthraldehyde thiosemicarbazone with human serum albumin was investigated at different temperatures using fluorescence and infrared spectrophotometry. The binding constant, K, for the reaction was determined using a number of different methods. Using a modified Stern-Volmer equation, K was determined to be 9.09×104,12.1×104, and 13.1×104 M−1 at 293 K, 298 K, and 308 K, respectively. A thermodynamic analysis showed that the reaction is spontaneous with ΔG being negative. The enthalpy of reaction ΔH=16.5 kJ mol−1 and the entropy of reaction ΔS=152 Jmol−1K−1. The values of ΔH and ΔS suggest that hydrophobic forces are dominant in the mode of interaction and that the process is mostly entropy driven.

  2. Microwave assisted synthesis, spectroscopic, electrochemical and DNA cleavage studies of lanthanide(III) complexes with coumarin based imines. (United States)

    Kapoor, Puja; Fahmi, Nighat; Singh, R V


    The present work stems from our interest in the synthesis, characterization and biological evaluation of lanthanide(III) complexes of a class of coumarin based imines which have been prepared by the interaction of hydrated lanthanide(III) chloride with the sodium salts of 3-acetylcoumarin thiosemicarbazone (ACTSZH) and 3-acetylcoumarin semicarbazone (ACSZH) in 1:3 molar ratio using thermal as well as microwave method. Characterization of the ligands as well as the metal complexes have been carried out by elemental analysis, melting point determinations, molecular weight determinations, magnetic moment, molar conductance, IR, (1)H NMR, (13)C NMR, electronic, EPR, X-ray powder diffraction and mass spectral studies. Spectral studies confirm ligands to be monofunctional bidentate and octahedral environment around metal ions. The redox behavior of one of the synthesized metal complex was investigated by cyclic voltammetry. Further, free ligands and their metal complexes have been screened for their antimicrobial as well as DNA cleavage activity. The results of these findings have been presented and discussed.

  3. Crystal structure of cis-bis[4-phenyl-2-(1,2,3,4-tetrahydronaphthalen-1-ylidenehydrazinecarbothioamidato-κ2N1,S]nickel(II monohydrate tetrahydrofuran disolvate

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    Adriano Bof de Oliveira


    Full Text Available The reaction of NiII acetate tetrahydrate with the ligand 4-phenyl-2-(1,2,3,4-tetrahydronaphthalen-1-ylidenehydrazinecarbothioamide in a 2:1 molar ratio yielded the title compound, [Ni(C16H16N3S2]·2C4H8O·H2O. The deprotonated ligands act as N,S-donors, forming five-membered metallacycles with the metal ion exhibiting a cis coordination mode unusual for thiosemicarbazone complexes. The NiII ion is four-coordinated in a tetrahedrally distorted square-planar geometry. Trans-arranged anagostic C—H...Ni interactions are observed. In the crystal, the complex molecules are linked by water molecules through N—H...O and O—H...S hydrogen-bonding interactions into centrosymmetric dimers stacked along the c axis, forming rings of graph-set R44(12. Classical O—H...O hydrogen bonds involving the water and tetrahydrofuran solvent molecules as well as weak C—H...π interactions are also present.

  4. Synthesis, spectral characterization, molecular modeling, thermal study and biological evaluation of transition metal complexes of a bidentate Schiff base ligand. (United States)

    Chandra, Sulekh; Bargujar, Savita; Nirwal, Rita; Qanungo, Kushal; Sharma, Saroj K


    Complexes of copper(II) and nickel(II) of general composition M(L)2X2, have been synthesized [where L=3-Bromoacetophenone thiosemicarbazone and X=CH3COO(-), Cl(-) and NO3(-)]. All the complexes were characterized by elemental analysis, magnetic moments, IR, electronic and EPR spectral studies. The ligand behaved as bidentate and coordinated through sulfur of -C=S group and nitrogen atoms of -C=N group. The copper(II) and nickel(II) complexes were found to have magnetic moments 1.94-2.02 BM, 2.96-3.02 BM respectively which was corresponding to one and two unpaired electrons respectively. The molar conductance of the complexes in solution of DMSO lies in the range of 10-20 Ω(-1) cm(2) mol(-1) indicating their non-electrolytic behavior. On the basis of EPR, electronic and infrared spectral studies, tetragonal geometry has been assigned for copper(II) complexes and an octahedral geometry for nickel(II) complexes. The values of Nephelauxetic parameter β lie in the range 0.19-0.37 which indicated the covalent character in metal ligand 'σ' bond. Synthesized ligand and its copper(II) and nickel(II) complexes have also been screened against different bacterial and fungal species which suggested that complexes are more active than the ligands in antimicrobial activities.


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    Vijay V. Dabholkar and Sunil R.Patil,Rajesh V. Pandey


    Full Text Available Quinoxaline-2,3(1H,4H-dione 1 was chlorinated by using SOCl2/DMF, to form 2,3- dichloroquinoxaline 2, The dichloro compound 2 was subjected to reaction with Substituted Triazole, 1,10-diaminonaphthalene, 2-aminothiophenol, o-phenylenediamine, 1,2- diaminoethane,Sodim azide, thiocarbohydrazones and thiosemicarbazones to furnish 3'- substituted-(1',2',4' triazolo [5,6-b] [quinoxalo (2,3-e]-1,3,4-thiadiazine 3a-c, Quinoxalino [1,4- b]-1,4-dihydronaphto[18-ef][1,4]-diazepine 4, 7-substituted-1,4-benzothiazino[2,3-b]- quinoxalines 5a-c, benzopiperazino[2,3-b]-quinoxalines 6 , piperazino[2,3-b]-quinoxalines 7, bis-triazo-[4,5-a/c]-quinoxalines 8, 2-(benzylidine-hyrazino-1,3,4-thiadiazino [ 5,6-b]- quinoxalines 9 and 2-(benzylidine-imino-1,3,3-thiadiazino [ 5,6-b]-quinoxalines 10 respectively. Representative samples were screened for their anti-microbial activity against gram-negative bacteria, E coli and Paeruginosa and gram-positive bacteria, S aureus, and C diphtheriae using disc diffusion method. The structures of the products were confirmed by IR,1H, 13 C NMR and elemental analysis.

  6. Structure-activity relationships for a class of selective inhibitors of the major cysteine protease from Trypanosoma cruzi. (United States)

    Guido, Rafael V C; Trossini, Gustavo H G; Castilho, Marcelo S; Oliva, Glaucius; Ferreira, Elizabeth I; Andricopulo, Adriano D


    Chagas' disease is a parasitic infection widely distributed throughout Latin America, with devastating consequences in terms of human morbidity and mortality. Cruzain, the major cysteine protease from Trypanosoma cruzi, is an attractive target for antitrypanosomal chemotherapy. In the present work, classical two-dimensional quantitative structure-activity relationships (2D QSAR) and hologram QSAR (HQSAR) studies were performed on a training set of 45 thiosemicarbazone and semicarbazone derivatives as inhibitors of T. cruzi cruzain. Significant statistical models (HQSAR, q(2) = 0.75 and r(2) = 0.96; classical QSAR, q(2) = 0.72 and r(2) = 0.83) were obtained, indicating their consistency for untested compounds. The models were then used to evaluate an external test set containing 10 compounds which were not included in the training set, and the predicted values were in good agreement with the experimental results (HQSAR, r(2)(pred) = 0.95; classical QSAR, r(2)(pred) = 0.91), indicating the existence of complementary between the two ligand-based drug design techniques.

  7. Inhibition of respiratory complex I by copper(ii)-bis(thiosemicarbazonato) complexes. (United States)

    Djoko, Karrera Y; Donnelly, Paul S; McEwan, Alastair G


    Several copper(ii) complexes of bis(thiosemicarbazones) [Cu(btsc)s] show promise as therapeutics for the treatment of neurological diseases, cancers and bacterial infections. These complexes are thought to act primarily as copper ionophores or "copper boosting" agents, whereby the Cu(II) centre is reduced by cytosolic reductants and Cu(I) is released as "free" or "bioavailable" ion. It is then assumed that the dissociated Cu(I) ion is the species responsible for many of the observed biological effects of Cu(btsc)s. We recently showed that Cu(btsc) complexes inhibited NADH dehydrogenases in the bacterial respiratory chain. In this work, we demonstrate that Cu(btsc) complexes also inhibit mitochondrial respiration and that Complex I in the mitochondrial electron transport chain is a specific target of inhibition. However, bioavailable Cu ions do not appear to contribute to the action of Cu(btsc) as a respiratory inhibitor. Instead, an intact Cu(btsc) molecule may bind reversibly and competitively to the site of ubiquinone binding in Complex I. Our results add to the growing body of evidence that the intact complex may be important in the overall cellular activity of Cu(btsc) complexes and further the understanding of their biological effects as a potential therapeutic.

  8. Simultaneous preconcentration of copper and mercury in water samples by cloud point extraction and their determination by inductively coupled plasma atomic emission spectrometry. (United States)

    Shoaee, Hamta; Roshdi, Mina; Khanlarzadeh, Nasibeh; Beiraghi, Asadollah


    A cloud-point extraction process coupled to ICP-OES by using 3-nitro benzaldehyde thiosemicarbazone (3-NBT) as complexing agent was developed for the simultaneous preconcentration and determination of copper and mercury in water samples. The variables affecting the complexation and extraction steps were optimized. Under the optimum conditions (i.e. 1.5×10(-5) mol L(-1) ligand, 0.3% (v/v) Triton X-114, 55 °C equilibrium temperature, incubation time of 30 min) the calibration graphs were linear in the range of 5-120 and 10-100 ng mL(-1) with enhancement factor of 82.7 and 51.3 for Cu(2+) and Hg(2+), respectively. The preconcentration factors were 28.6 in both cases and detection limits were obtained 0.48 for Cu and 1.1 ng mL(-1) for Hg. The precisions (R.S.D.%) for five replicate determinations at 50 ng mL(-1) of copper and mercury were better than 1.8% and 3.2%, respectively. The accuracy of the proposed method is validated by analyzing a certified reference material of water (RTC-QCI-049) with satisfactory results. Finally, the proposed method was utilized successfully for the determination of copper and mercury in surface water (river), tap water and bottled mineral water samples.

  9. Hexa-kis-(μ3-2-hy-droxy-naphthalene-1-carboxaldehyde thio-semicarbazonato-κ(3) N (2):S:S)hexa-silver(I) N,N-dimethyl-formamide tetra-solvate. (United States)

    Sun, Qiaozhen; Chai, Liyuan; Liu, Hui; Wang, Junke


    In the title compound, [Ag6(C12H10N3OS)6]·4C3H7NO, the hexa-nuclear complex mol-ecule lies about an inversion center. The six Ag atoms form a distorted octa-hedron, with Ag⋯Ag distances in the range 2.933 (1)-3.401 (1) Å. Each Ag atom is surrounded by one N atom and two thiol-ate S atoms from two deprotonated 2-hy-droxy-1-naphthaldehyde thio-semi-carb-a-zone ligands. Each ligand coordinates three Ag atoms via a bridging thiol-ate S atom and a monodentate N atom, thus two Ag3S3 hexa-gonal rings are linked together. Two dimethyl-formamide solvent mol-ecules are located in four sets of sites with half-occupancy and form O⋯H-N hydrogen bonds to the complex mol-ecule. Intra-molecular O-H⋯N hydrogen bonds are also present. The discrete hexa-nuclear clusters are further linked through π-π inter-actions into layers parallel to (001), the shortest distance between the centroids of aromatic rings being 3.698 (2) Å.

  10. Microwave assisted synthesis, characterization and biological evaluation of palladium and platinum complexes with azomethines (United States)

    Sharma, Krishna; Singh, Ritu; Fahmi, Nighat; Singh, R. V.


    Reactions of 3-acetyl-2,5-dimethylthiophene with thiosemicarbazide and semicarbazide hydrochloride resulted in the formation of new heterocyclic ketimines, 3-acetyl-2,5-dimethylthiophene thiosemicarbazone (C 9H 13N 3OS 2 or L 1H) and 3-acetyl-2,5- dimethylthiophene semicarbazone (C 9H 13N 3OS or L 2H), respectively. The Pd(II) and Pt(II) complexes have been synthesized by mixing metal salts in 1:2 molar ratios with these ligands by using microwave as well as conventional heating method for comparison purposes. The authenticity of these ligands and their complexes has been established on the basis of elemental analysis, melting point determinations, molecular weight determinations, IR, 1H NMR and UV spectral studies. These studies showed that the ligands coordinate to the metal atom in a monobasic bidentate manner and square planar environment around the metal atoms has been proposed to the complexes. Both the ligands and their complexes have been screened for their antimicrobial activities. The antiamoebic activity of both the ligands and their palladium compounds against the protozoan parasite Entamoeba histolytica has been tested.

  11. Synthesis, Characterization, and Biological Studies of Binuclear Copper(II Complexes of (2E-2-(2-Hydroxy-3-Methoxybenzylidene-4N-Substituted Hydrazinecarbothioamides

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    P. Murali Krishna


    Full Text Available Four novel binuclear copper(II complexes [1–4] of (2E-2-(2-hydroxy-3-methoxybenzylidene-4N-substituted hydrazinecarbothioamides, (OH(OCH3C6H4CH=NNHC(SNHR, where R = H (L1, Me (L2, Et (L3, or Ph (L4, have been synthesized and characterized. The FT-IR spectral data suggested the attachment of copper(II ion to ligand moiety through the azomethine nitrogen, thioketonic sulphur, and phenolic-O. The spectroscopic characterization indicates the dissociation of dimeric complex into mononuclear [Cu(LCl] units in polar solvents like DMSO, where L is monoanionic thiosemicarbazone. The DNA binding properties of the complexes with calf thymus (CT DNA were studied by spectroscopic titration. The complexes show binding affinity to CT DNA with binding constant (Kb values in the order of 106 M−1. The ligands and their metal complexes were tested for antibacterial and antifungal activities by agar disc diffusion method. Except for complex 4, all complexes showed considerable activity almost equal to the activity of ciprofloxacin. These complexes did not show any effect on Gram-negative bacteria, whereas they showed moderate activity for Gram-positive strains.


    Institute of Scientific and Technical Information of China (English)


    New Schiff base polymers poly[4,4'-methylenebis(cinnamaldehyde)ethylenediimine] (PMBCen), poly[4,4'-methylenebis(cinnamaldehyde)1,2-propylenediimine] (PMBCPn), poly[4,4'-methylenebis(cinnamaldehyde)1,3-propylenediimine] (PMBCPR), poly[4,4'-methylenebis(cinnamaldehyde) 1,2-phenylenediimine] (PMBCPh), poly[4,4'-methylenebis(cinnamaldehyde)meso-stilbenediimine] (PMBCS), poly[4,4'-methylenebis(cinnamaldehyde)urea] (PMBCUR), poly[4,4'-methylenebis(cinnamaldehyde)semicarbazone] (PMBCSc), poly[4,4'-methylenebis(cinnamaldehyde)thiosemicarbazone](PMBCTSc) and poly[4,4'-methylenebis(cinnamaldehyde)hydrazone] (PMBCH) were formed by polycondensation of 4,4'-methylenebis(cinnamaldehyde) with ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2-phenylenediamine, meso-stilbenediamine, urea, semicarbazide, thiosemicarbazide and hydrazine, respectively. The dialdehyde and polymers have been characterized through elemental micro-analysis, IR, UV-Vis and 1H-NMR spectroscopic techniques. Thermoanalytical studies and viscous flow of dilute solutions of dialdehyde and its polymers have been examined and compared.

  13. Synthesis, in vitro β-glucuronidase inhibitory activity and in silico studies of novel (E)-4-Aryl-2-(2-(pyren-1-ylmethylene)hydrazinyl)thiazoles. (United States)

    Salar, Uzma; Khan, Khalid Mohammed; Syed, Shazia; Taha, Muhammad; Ali, Farman; Ismail, Nor Hadiani; Perveen, Shahnaz; Wadood, Abdul; Ghufran, Mehreen


    Current research is based on the synthesis of novel (E)-4-aryl-2-(2-(pyren-1-ylmethylene)hydrazinyl)thiazole derivatives (3-15) by adopting two steps route. First step was the condensation between the pyrene-1-carbaldehyde (1) with the thiosemicarbazide to afford pyrene-1-thiosemicarbazone intermediate (2). While in second step, cyclization between the intermediate (2) and phenacyl bromide derivatives or 2-bromo ethyl acetate was carried out. Synthetic derivatives were structurally characterized by spectroscopic techniques such as EI-MS, (1)H NMR and (13)C NMR. Stereochemistry of the iminic double bond was confirmed by NOESY analysis. All pure compounds 2-15 were subjected for in vitro β-glucuronidase inhibitory activity. All molecules were exhibited excellent inhibition in the range of IC50=3.10±0.10-40.10±0.90μM and found to be even more potent than the standard d-saccharic acid 1,4-lactone (IC50=48.38±1.05μM). Molecular docking studies were carried out to verify the structure-activity relationship. A good correlation was perceived between the docking study and biological evaluation of active compounds.


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    Full Text Available In this paper, new synthesized three azomethine derivatives applied in dyeing textiles checking the anti-microbial properties of active components, at the same time [1-3]. The emphasis is thrown on the verification of anti-microbial properties that are important for obtaining textile with significantly improved performance. All compounds were characterized and evaluated for their anti-microbial activity against 7 pathogenic bacteria, 1 parasitic protozoan and 1 fungus. It estimated anti-bacterial activity in vitro against the following microorganisms Staphylococcus aureus, Bacillus anthracis, Streptococcus faecalis, Enterobacter sp., Escherichia coli, Pseudomonas aeruginosa, Proteus mirabilis, and Candida albicans. 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 synthesized azomethines, showed very good substantivity for wool fibers, gave fine coloring, with good degree of exhaustion after dyeing. The combination of extended synthetic analogues of natural molecules leads to discovery of chemical entities which might be excellent anti-microbial and anti-amoebic compounds as depicted in our results. Being highly the effects this compound can be explored in future as an option for decreasing pathogenic potential of infecting from different sources. Azomethines containing hydrazone (dyestuff 1 and phenylhydrazone (dyestuff 2 as moiety show average yield and moderate inhibition activity while azomethines containing thiosemicarbazone (dyestuff 3 as moiety show higher yield and greater inhibition activity towards gram-negative and gram-positive bacteria as well as a fungus.

  15. A metal-organic tetrahedron as a redox vehicle to encapsulate organic dyes for photocatalytic proton reduction. (United States)

    Jing, Xu; He, Cheng; Yang, Yang; Duan, Chunying


    The design of artificial systems that mimic highly evolved and finely tuned natural photosynthetic systems is a subject of intensive research. We report herein a new approach to constructing supramolecular systems for the photocatalytic generation of hydrogen from water by encapsulating an organic dye molecule into the pocket of a redox-active metal-organic polyhedron. The assembled neutral Co4L4 tetrahedron consists of four ligands and four cobalt ions that connect together in alternating fashion. The cobalt ions are coordinated by three thiosemicarbazone NS chelators and exhibit a redox potential suitable for electrochemical proton reduction. The close proximity between the redox site and the photosensitizer encapsulated in the pocket enables photoinduced electron transfer from the excited state of the photosensitizer to the cobalt-based catalytic sites via a powerful pseudo-intramolecular pathway. The modified supramolecular system exhibits TON values comparable to the highest values reported for related cobalt/fluorescein systems. Control experiments based on a smaller tetrahedral analogue of the vehicle with a filled pocket and a mononuclear compound resembling the cobalt corner of the tetrahedron suggest an enzymatic dynamics behavior. The new, well-elucidated reaction pathways and the increased molarity of the reaction within the confined space render these supramolecular systems superior to other relevant systems.

  16. Microwave assisted synthesis, characterization and biological evaluation of palladium and platinum complexes with azomethines. (United States)

    Sharma, Krishna; Singh, Ritu; Fahmi, Nighat; Singh, R V


    Reactions of 3-acetyl-2,5-dimethylthiophene with thiosemicarbazide and semicarbazide hydrochloride resulted in the formation of new heterocyclic ketimines, 3-acetyl-2,5-dimethylthiophene thiosemicarbazone (C(9)H(13)N(3)OS(2) or L(1)H) and 3-acetyl-2,5- dimethylthiophene semicarbazone (C(9)H(13)N(3)OS or L(2)H), respectively. The Pd(II) and Pt(II) complexes have been synthesized by mixing metal salts in 1:2 molar ratios with these ligands by using microwave as well as conventional heating method for comparison purposes. The authenticity of these ligands and their complexes has been established on the basis of elemental analysis, melting point determinations, molecular weight determinations, IR, (1)H NMR and UV spectral studies. These studies showed that the ligands coordinate to the metal atom in a monobasic bidentate manner and square planar environment around the metal atoms has been proposed to the complexes. Both the ligands and their complexes have been screened for their antimicrobial activities. The antiamoebic activity of both the ligands and their palladium compounds against the protozoan parasite Entamoeba histolytica has been tested.

  17. Crystal structure of 1-{(Z-[(2E-3-(4-chlorophenyl-1-phenylprop-2-en-1-ylidene]amino}-3-ethylthiourea

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    Ming Yueh Tan


    Full Text Available In the title thiosemicarbazone compound, C18H18ClN3S, the CN3S residue is almost planar (r.m.s. deviation = 0.0031 Å and forms dihedral angles of 65.99 (7 and 34.60 (10° with the phenyl and chlorobenzene rings, respectively; the dihedral angle between the aromatic rings is 85.13 (8°. The conformation about the C=N bond is Z, and that about the C=C bonds is E. The imine N and ethyl N atoms are syn and are linked by an ethyl–imine N—H...N hydrogen bond. This H atom also forms an intermolecular hydrogen bond to the thione S atom, resulting in a supramolecular helical chain propagating along the b axis. The chains are consolidated into a three-dimensional architecture by phenyl-C—H...Cl contacts and weak π–π interactions between centrosymmetrically related chlorobenzene rings [inter-centroid distance = 3.9127 (15 Å].

  18. Passive diffusion of naltrexone into human and animal cells and upregulation of cell proliferation. (United States)

    Cheng, Fan; McLaughlin, Patricia J; Banks, William A; Zagon, Ian S


    Naltrexone (NTX) is a potent opioid antagonist that promotes cell proliferation by upregulating DNA synthesis through displacement of the tonically active inhibitory peptide, opioid growth factor (OGF) from its receptor (OGFr). To investigate how NTX enters cells, NTX was fluorescently labeled [1-(N)-fluoresceinyl NTX thiosemicarbazone; FNTX] to study its uptake by living cultured cells. When human head and neck squamous cell carcinoma cell line (SCC-1) was incubated with FNTX for as little as 1 min, cells displayed nuclear and cytoplasmic staining of FNTX as determined by fluorescent deconvolution microscopy, with enrichment of fluorescent signal in the nucleus and nucleolus. The same temporal-spatial distribution of FNTX was detected in a human pancreatic cancer cell line (MIA PaCa-2), African green monkey kidney cell line (COS-7), and human mesenchymal stem cells (hMSCs). FNTX remained in cells for as long as 48 h. FNTX was internalized in SCC-1 cells when incubation occurred at 4 degrees C, with the signal being comparable to that recorded at 37 degrees C. A 100-fold excess of NTX or a variety of other opioid ligands did not alter the temporal-spatial distribution of FNTX. Neither fluorescein-labeled dextran nor fluorescein alone entered the cells. To study the effect of FNTX on DNA synthesis, cells incubated with FNTX at concentrations ranging from 10(-5) to 10(-8) M had a 5-bromo-2'-deoxyuridine index that was 39-82% greater than for vehicle-treated cells and was comparable to that of unlabeled NTX (37-70%). Taken together, these results suggested that NTX enters cells by passive diffusion in a nonsaturable manner.

  19. 8-Hydroxyquinoline Schiff-base compounds as antioxidants and modulators of copper-mediated Aβ peptide aggregation. (United States)

    Gomes, Luiza M F; Vieira, Rafael P; Jones, Michael R; Wang, Michael C P; Dyrager, Christine; Souza-Fagundes, Elaine M; Da Silva, Jeferson G; Storr, Tim; Beraldo, Heloisa


    One of the hallmarks of Alzheimer's disease (AD) in the brain are amyloid-β (Aβ) plaques, and metal ions such as copper(II) and zinc(II) have been shown to play a role in the aggregation and toxicity of the Aβ peptide, the major constituent of these extracellular aggregates. Metal binding agents can promote the disaggregation of Aβ plaques, and have shown promise as AD therapeutics. Herein, we describe the syntheses and characterization of an acetohydrazone (8-H2QH), a thiosemicarbazone (8-H2QT), and a semicarbazone (8-H2QS) derived from 8-hydroxyquinoline. The three compounds are shown to be neutral at pH7.4, and are potent antioxidants as measured by a Trolox Equivalent Antioxidant Capacity (TEAC) assay. The ligands form complexes with Cu(II), 8-H2QT in a 1:1 metal:ligand ratio, and 8-H2QH and 8-H2QS in a 1:2 metal:ligand ratio. A preliminary aggregation inhibition assay using the Aβ1-40 peptide showed that 8-H2QS and 8-H2QH inhibit peptide aggregation in the presence of Cu(II). Native gel electrophoresis/Western blot and TEM images were obtained to give a more detailed picture of the extent and pathways of Aβ aggregation using the more neurotoxic Aβ1-42 in the presence and absence of Cu(II), 8-H2QH, 8-H2QS and the drug candidate PBT2. An increase in the formation of oligomeric species is evident in the presence of Cu(II). However, in the presence of ligands and Cu(II), the results match those for the peptide alone, suggesting that the ligands function by sequestering Cu(II) and limiting oligomer formation in this assay.

  20. Studies of ion-imprinted polymers for solid-phase extraction of ruthenium from environmental samples before its determination by electrothermal atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Zambrzycka, Elzbieta; Roszko, Dorota; Lesniewska, Barbara; Wilczewska, Agnieszka Z.; Godlewska-Zylkiewicz, Beata, E-mail:


    The examination of the effect of interfering ions on the analytical signal of ruthenium measured by electrothermal atomic absorption spectrometry was initially performed in this work. The complexes of ruthenium(III) with thiosemicarbazide (TSd) and acetaldehyde thiosemicarbazone (AcTSn) were prepared and imprinted in polymeric network. The ion-imprinted polymers were synthesized by copolymerization of methacrylic acid, as functional monomer and ethylene glycol dimethacrylate, as crosslinking agent in the presence of 2,2-azobisisobutyronitrile as initiator. The effects of sample volume, pH, and flow rate on the extraction of analyte were studied in dynamic mode. The optimum pH for quantitative retention of ruthenium on each of the studied sorbents was 7.5 {+-} 0.5. The elution of analyte was completed with 0.2 mol L{sup -1} thiourea in 0.2 mol L{sup -1} HCl. The effect of matrix ions on ruthenium(III) separation process was studied. The analytical performance of the Ru-TSd polymer in the presence of competing ions was better than Ru-AcTSn polymer, considering recovery of analyte, reproducibility of results, selectivity coefficients, and sorbent capacity. The detection limit of the proposed method (0.16 ng mL{sup -1} on Ru-TSd and 0.25 ng mL{sup -1} on Ru-AcTSn) is lower in comparison with the previously published methods. The developed separation method was successfully applied to the determination of trace amounts of ruthenium in spiked water samples, sludge, grass, and human hair.

  1. Increasing intracellular bioavailable copper selectively targets prostate cancer cells. (United States)

    Cater, Michael A; Pearson, Helen B; Wolyniec, Kamil; Klaver, Paul; Bilandzic, Maree; Paterson, Brett M; Bush, Ashley I; Humbert, Patrick O; La Fontaine, Sharon; Donnelly, Paul S; Haupt, Ygal


    The therapeutic efficacy of two bis(thiosemicarbazonato) copper complexes, glyoxalbis[N4-methylthiosemicarbazonato]Cu(II) [Cu(II)(gtsm)] and diacetylbis[N4-methylthiosemicarbazonato]Cu(II) [Cu(II)(atsm)], for the treatment of prostate cancer was assessed in cell culture and animal models. Distinctively, copper dissociates intracellularly from Cu(II)(gtsm) but is retained by Cu(II)(atsm). We further demonstrated that intracellular H2gtsm [reduced Cu(II)(gtsm)] continues to redistribute copper into a bioavailable (exchangeable) pool. Both Cu(II)(gtsm) and Cu(II)(atsm) selectively kill transformed (hyperplastic and carcinoma) prostate cell lines but, importantly, do not affect the viability of primary prostate epithelial cells. Increasing extracellular copper concentrations enhanced the therapeutic capacity of both Cu(II)(gtsm) and Cu(II)(atsm), and their ligands (H2gtsm and H2atsm) were toxic only toward cancerous prostate cells when combined with copper. Treatment of the Transgenic Adenocarcinoma of Mouse Prostate (TRAMP) model with Cu(II)(gtsm) (2.5 mg/kg) significantly reduced prostate cancer burden (∼70%) and severity (grade), while treatment with Cu(II)(atsm) (30 mg/kg) was ineffective at the given dose. However, Cu(II)(gtsm) caused mild kidney toxicity in the mice, associated primarily with interstitial nephritis and luminal distention. Mechanistically, we demonstrated that Cu(II)(gtsm) inhibits proteasomal chymotrypsin-like activity, a feature further established as being common to copper-ionophores that increase intracellular bioavailable copper. We have demonstrated that increasing intracellular bioavailable copper can selectively kill cancerous prostate cells in vitro and in vivo and have revealed the potential for bis(thiosemicarbazone) copper complexes to be developed as therapeutics for prostate cancer.

  2. Ensemble-Based Virtual Screening Led to the Discovery of New Classes of Potent Tyrosinase Inhibitors. (United States)

    Choi, Joonhyeok; Choi, Kwang-Eun; Park, Sung Jean; Kim, Sun Yeou; Jee, Jun-Goo


    In this study, we report new classes of potent tyrosinase inhibitors identified by enhanced structure-based virtual screening prediction; the enzyme and melanin content assays were also confirmed. Tyrosinase, a type-3 copper protein, participates in two distinct reactions, hydroxylation of tyrosine to DOPA and conversion of DOPA to dopaquinone, in melanin biosynthesis. Although numerous inhibitors of this reaction have been reported, there is a lag in the discovery of the new functional moieties. In order to improve the performance of virtual screening, we first produced an ensemble of 10,000 structures using molecular dynamics simulation. Quantum mechanical calculation was used to determine the partial charges of catalytic copper ions based on the met and deoxy states. Second, we selected a structure showing an optimal receiver operating characteristic (ROC) curve with known direct binders and their physicochemically matched decoys. The structure revealed more than 10-fold higher enrichment at 1% of the ROC curve than those observed in X-ray structures. Third, high-throughput virtual screening with DOCK 3.6 was performed using a library consisting of approximately 400,000 small molecules derived from the ZINC database. Fourth, we obtained the top 60 molecules and tested their inhibition of mushroom tyrosinase. The extended assays included 21 analogs of the 21 initial hits to test their inhibition properties. Here, the moieties of tetrazole and triazole were identified as new binding cores interacting with the dicopper catalytic center. All 42 inhibitors showed inhibitory constant, Ki, values ranging from 11.1 nM and 33.4 μM, with a tetrazole compound exhibiting the strongest activity. Among the 42 molecules, five displayed more than 30% reduction in melanin production when treated in B16F10 melanoma cells; cell viability was >90% at 20 μM. Particularly, a thiosemicarbazone-containing compound reduced melanin content by 55%.

  3. Subcellular localization of a fluorescent derivative of CuII(atsm) offers insight into the neuroprotective action of CuII(atsm). (United States)

    Price, Katherine Ann; Crouch, Peter J; Lim, SinChun; Paterson, Brett M; Liddell, Jeffrey R; Donnelly, Paul S; White, Anthony R


    Copper complexes of bis(thiosemicarbazone) (Cu(II)(btsc)s) have been studied as potential anti-cancer agents and hypoxia imaging agents. More recently, Cu(II)(btsc)s have been identified as possessing potent neuroprotective properties in cell and animal models of neurodegenerative disease. Despite their broad range of pharmacological activity little is known about how cells traffic Cu(II)(btsc)s and how this relates to potential anti-cancer or neuroprotective outcomes. One method of investigating sub-cellular localization of metal complexes is through confocal fluorescence imaging of the compounds in cells. Previously we harnessed the fluorescence of a pyrene group attached to diacetyl-bis(N4-methylthiosemicarbazonato)copper(ii)) (Cu(II)(atsm)), (Cu(II)L(1)). We demonstrated that Cu(II)L(1) was partially localized to lysosomes in HeLa cancer epithelial cells. Here we extend these studies to map the sub-cellular localization of Cu(II)L(1) in M17 neuroblastoma cells. Treatment of M17 or HeLa cells led to rapid association of the Cu-complex into distinct punctate structures that partially co-localized with lysosomes as assessed by co-localization with Lysotracker and acridine orange. No localization to early or late endosomes, the nucleus or mitochondria was observed. We also found evidence for a limited association of Cu(II)L(1) with autophagic structures, however, this did not account for the majority of the punctate localization of Cu(II)L(1). In addition, Cu(II)L(1) revealed partial localization with ER Tracker and was found to inhibit ER stress induced by tunicamycin. This is the first report to comprehensively characterize the sub-cellular localization of a Cu(II)(atsm) derivative in cells of a neuronal origin and the partial association with lysosome/autophagic structures and the ER may have a potential role in neuroprotection.

  4. Heteroleptic complexes of Zn(II) based on 1-(5-bromo-2-hydroxybenzylidene)-4-phenylthiosemicarbazide: Synthesis, structural characterization, theoretical studies and antibacterial activity (United States)

    Azarkish, Mohammad; Akbari, Alireza; Sedaghat, Tahereh; Simpson, Jim


    Four new ternary complexes, [ZnL (2,2‧-bipy)] (1), Zn2L2(4,4‧-bipy)] (2), [ZnL(Imd)]·H2O (3) and [ZnL3(MeImd)] (4), have been synthesized from the reaction of Zn(II) acetate with 1-(5-bromo-2-hydroxybenzylidene)-4-phenylthiosemicarbazide (H2L) in the presence of a heterocyclic base, 2,2‧-bipyridine, 4,4‧-bipyridine, imidazole or 2-methylimidazole, as an auxiliary ligand. The complexes have been investigated by elemental analysis and FT-IR, UV-Vis and 1HNMR spectroscopy. These data show that the thiosemicarbazone acts as a tridentate dianionic ligand and coordinates via the thiol group, imine nitrogen, and phenolic oxygen. The coordination sphere was completed by the nitrogen atom(s) of the secondary ligand. The structure of 1 was also confirmed by X-ray crystallography and shown to be a five coordinate complex with coordination geometry between the square-pyramidal and trigonal-bipyramidal. Density functional theory (DFT) calculations including geometry optimization, vibrational frequencies and electronic absorptions have been performed for 1 with the B3LYP functional at the TZP(6-311G*) basis set using the Gaussian 03 or ADF 2009 packages. The optimization calculation showed that the crystallographically determined geometry parameters can be reproduced with that basis set. Experimental IR frequencies and calculated vibration frequencies also support each other. The in vitro antibacterial activities of the ligand and complexes have been evaluated against Gram-positive (B. subtilis and S. aureus) and Gram-negative (P. aeruginosa) bacteria and compared with the standard antibacterial drugs. The results reveal that all of the complexes show much better activity in comparison to the individual thiosemoicarbazone ligand (H2L), against all bacterial strains used, with complex 3 showing the most promising results.

  5. 双二茂铁-钯配合物的合成,结构和电化学%Synthesis, Crystal Structure and Electrochemistry of Biferrocene Palladium Complex

    Institute of Scientific and Technical Information of China (English)

    陈光; 区升举; 白志平; 韩刚; 段春迎


    A new supramolecular cyclohexane-like structure [PdL2] 6 (HL= acetylferrocenyl thiosemicarbazone) has been in a distorted square-planar cis-configuration in which two ferrocene-containing ligands positioned on the same side.Each ferrocene moieties interacts with symmetry-related species to form a two dimensions supramolecular network.Electrochemical measurements of [ PdL 2 ], [NiL 2 ] and [ZnL 2 ] compounds indicate that the square planar configuration of the Ni (Ⅱ) and Pd (Ⅱ) moieties, can effectively transmit the redox effects of the ferrocene moieties.%本文讨论了由二茂铁的C-H…π作用组装的具有类环己烷结构的氨基硫脲钯金属配合物的结构和电化学性能.晶体结构中钯原子以顺式平面正方形的构型分别与两个氨基硫脲配体配位,两个配体中的二茂铁基团位于钯原子同一侧,每个二茂铁与相邻分子中的二茂铁基团通过环戊二烯基环间的C-H…π作用形成由类环己烷结构连结的二维网状结构.对钯的配合物及相关的镍和锌配合物的电化学研究表明,平面正方型的钯和镍可以有效的传递两个茂铁间的氧化-还原性能.

  6. A comparison of PET imaging characteristics of various copper radioisotopes

    Energy Technology Data Exchange (ETDEWEB)

    Williams, Heather Ann [North Western Medical Physics, Christie Hospital NHS Trust, Manchester (United Kingdom); University of Manchester Institute of Science and Technology, Department of Instrumentation and Analytical Science, Manchester (United Kingdom); Robinson, Simon; Julyan, Peter; Hastings, David [North Western Medical Physics, Christie Hospital NHS Trust, Manchester (United Kingdom); Zweit, Jamal [University of Manchester Institute of Science and Technology, Department of Instrumentation and Analytical Science, Manchester (United Kingdom); Paterson Institute for Cancer Research, Radiochemical Targeting and Imaging, Manchester (United Kingdom)


    PET radiotracers which incorporate longer-lived radionuclides enable biological processes to be studied over many hours, at centres remote from a cyclotron. This paper examines the radioisotope characteristics, imaging performance, radiation dosimetry and production modes of the four copper radioisotopes, {sup 60}Cu,{sup 61}Cu,{sup 62}Cu and{sup 64}Cu, to assess their merits for different PET imaging applications. Spatial resolution, sensitivity, scatter fraction and noise-equivalent count rate (NEC) are predicted for{sup 60}Cu,{sup 61}Cu,{sup 62}Cu and{sup 64}Cu using a model incorporating radionuclide decay properties and scanner parameters for the GE Advance scanner. Dosimetry for{sup 60}Cu,{sup 61}Cu and{sup 64}Cu is performed using the MIRD model and published biodistribution data for copper(II) pyruvaldehyde bis(N{sup 4}-methyl)thiosemicarbazone (Cu-PTSM). {sup 60}Cu and{sup 62}Cu are characterised by shorter half-lives and higher sensitivity and NEC, making them more suitable for studying the faster kinetics of small molecules, such as Cu-PTSM.{sup 61}Cu and{sup 64}Cu have longer half-lives, enabling studies of the slower kinetics of cells and peptides and prolonged imaging to compensate for lower sensitivity, together with better spatial resolution, which partially compensates for loss of image contrast.{sup 61}Cu-PTSM and{sup 64}Cu-PTSM are associated with radiation doses similar to [{sup 18}F]-fluorodeoxyglucose, whilst the doses for{sup 60}Cu-PTSM and{sup 62}Cu-PTSM are lower and more comparable with H{sub 2}{sup 15}O. The physical and radiochemical characteristics of the four copper isotopes make each more suited to some imaging tasks than others. The results presented here assist in selecting the preferred radioisotope for a given imaging application, and illustrate a strategy which can be extended to the majority of novel PET tracers. (orig.)

  7. Plasmodium serine hydroxymethyltransferase as a potential anti-malarial target: inhibition studies using improved methods for enzyme production and assay

    Directory of Open Access Journals (Sweden)

    Sopitthummakhun Kittipat


    as inhibitors of malarial dihydrofolate reductase. Plasmodium SHMT was slowly inactivated by thiosemicarbazide and formed a covalent intermediate, PLP-thiosemicarbazone. Conclusions Auto-induction media offers a cost-effective method for the production of Plasmodium SHMTs and should be applicable for other Plasmodium enzymes. The SHMT-MTHFD coupled assay is equivalent to the SHMT-MTHFR coupled assay, but is more convenient for inhibitor screening and other studies of the enzyme. In addition to inhibitors of malarial SHMT, the development of species-specific, anti-SHMT inhibitors is plausible due to the presence of differential active sites on the Plasmodium enzymes.

  8. Mechanistic studies of semicarbazone triapine targeting human ribonucleotide reductase in vitro and in mammalian cells: tyrosyl radical quenching not involving reactive oxygen species. (United States)

    Aye, Yimon; Long, Marcus J C; Stubbe, JoAnne


    Triapine® (3-aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP)) is a drug in Phase II trials. One of its established cellular targets is the β(2) subunit of ribonucleotide reductase that requires a diferric-tyrosyl-radical [(Fe(III)(2)-Y·)(Fe(III)(2))] cofactor for de novo DNA biosynthesis. Several mechanisms for 3-AP inhibition of β(2) have been proposed; one involves direct iron chelation from β(2), whereas a second involves Y· destruction by reactive oxygen species formed in situ in the presence of O(2) and reductant by Fe(II)-(3-AP). Inactivation of β(2) can thus arise from cofactor destruction by loss of iron or Y·. In vitro kinetic data on the rates of (55)Fe and Y· loss from [((55)Fe(III)(2)-Y·)((55)Fe(III)(2))]-β(2) under aerobic and anaerobic conditions reveal that Y· loss alone is sufficient for rapid β(2) inactivation. Oxyblot(TM) and mass spectrometric analyses of trypsin-digested inhibited β(2), and lack of Y· loss from H(2)O(2) and O(2)(•) treatment together preclude reactive oxygen species involvement in Y· loss. Three mammalian cell lines treated with 5 μm 3-AP reveal Y· loss and β(2) inactivation within 30-min of 3-AP-exposure, analyzed by whole-cell EPR and lysate assays, respectively. Selective degradation of apo- over [(Fe(III)(2)-Y·)(Fe(III)(2))]-β(2) in lysates, similar iron-content in β(2) immunoprecipitated from 3-AP-treated and untreated [(55)Fe]-prelabeled cells, and prolonged (12 h) stability of the inhibited β(2) are most consistent with Y· loss being the predominant mode of inhibition, with β(2) remaining iron-loaded and stable. A model consistent with in vitro and cell-based biochemical studies is presented in which Fe(II)-(3-AP), which can be cycled with reductant, directly reduces Y· of the [(Fe(III)(2)-Y·)(Fe(III)(2))] cofactor of β(2).

  9. Organometallic complexes of the platinum metals: Synthesis, structure, and catalytic applications

    Indian Academy of Sciences (India)

    Piyali Paul; Samaresh Bhattacharya


    Reaction of a group of N-(aryl)picolinamides (pic-R) with [Ru(PPh3)2(CO)2Cl2] in refluxing 2-methoxyethanol in the presence of a base affords hydrido complexes of two types (1-R and 2-R), which are geometric isomers. Similar reaction with N-(naphthyl)picolinamide (pic-nap) yields an organoruthenium complex (3) via formation of a hydrido intermediate. Reaction of 2-(arylazo)phenols (ap-R) with [Ir(PPh3)3Cl] in refluxing ethanol affords a mono-hydrido intermediate (4-R), a di-hydrido intermediate (5-R) and an organoiridium complex (6-R) as the final product, where the azo-ligand is coordinated as CNO-donor. Reaction of ap-R ligands with [Rh(PPh3)3Cl] yields organorhodium complexes (7-R) analogous to 6-R, but without any hydrido intermediate. N-(2'-hydroxyphenyl)benzaldimines (hpbz-R) react with [Rh(PPh3)3Cl] to yield a group of organorhodium complexes (8-R), where the hpbz-R ligands are coordinated in CNO-fashion. Upon interaction with [Ir(PPh3)3Cl] 2-(2',6'-dimethylphenylazo)-4-methylphenol (dmap) undergoes a methyl C-H activation and affords organoiridium complex 9, while 2-(2'-methylphenylazo)-4-methylphenol (mmap) undergoes a phenyl C-H activation and gives organoiridium complex 10. Reaction of benzaldehyde thiosemicarbazones (bztsc-R) with [Pd(PPh3)2Cl2], carried out with the expectation of inducing CNS-mode of coordination, actually has yielded complexes (11-R) where the bztsc-R is coordinated in an uncommon NS-mode forming a fivemembered chelate ring associated with a restricted rotation around the imine (C=N) bond. These palladium complexes are found to catalyse C-C cross coupling reactions very efficiently. Crystal structures of selected complexes of each type have been determined by X-ray crystallography.

  10. 噻吩-N-4甲基缩氨基硫脲及其银离子配合物对EC109增殖和凋亡影响%Effects of thiophene-2-carboxaldehyde N(4)-methylthiosemicarbazone and its Ag(Ⅰ)complex on proliferation and apoptosis of EC109

    Institute of Scientific and Technical Information of China (English)

    李晓娟; 曹更生; 刘广超; 李明雪; 张洪


    Aim To study the anti-tumor activity and the possible mechanism of thiophene-2-carboxaldehydeN( 4 )-methylthiosemicarbazone and its Ag( Ⅰ ) complex for esophageal EC109 in vitro. Methods The effect of the thiophene-2-carboxaldehydeN( 4 ) -methyl thiosemicarbazone and its Ag( Ⅰ ) complex on cell proliferation for esophageal EC109 in vitro was tested by MTT method. Ciemsa staining and acridine orange ( AO ) fluorescence staining were used to observe the morphological changes of the esophageal EC109. Cell apoptosis and cell cycle distribution were detected by flow cytometry. Results The results indicated its Ag ( Ⅰ ) complex had strong inhibitory effect on EC109 cell proliferation in a dose-and-time dependent manner;Typical morphological changes of apoptosis were also observed in the esophageal EC109. The result of flow cytometry showed the Ag( Ⅰ ) complex led to cell apoptosis partly in lower concentrations . And the apoptosis increased in a concentration dependent manner, and inhibited G0/G1 phase from entering S phase. Conclusions The ligand N has no anti-tumor effect at all on esophageal EC109 , but the Ag( Ⅰ )complex N-Ag exhibits significant anti-tumor activity after introducing Ag ion, and possibly induces cell apoptosis by blocking cell cycle.%目的 用食管癌细胞EC109体外鉴定噻吩-N-4甲基缩氨基硫脲(N)及其过渡金属配合物噻吩-N-4甲基缩氨基硫脲银(N-Ag)的抗肿瘤生物活性,探讨其可能机制.方法 采用四甲基偶氮唑法(MTT法)测定上述两种药物体外对食道癌细胞EC109生长抑制率;采用吖啶橙荧光染色和吉姆萨染色观察药物对食道癌细胞EC109形态影响;采用流式细胞仪检测细胞周期的改变和细胞的凋亡情况.结果 N-Ag对食道癌EC109的增殖有较强的抑制作用,且成量效和时效关系;实验组能观察到细胞凋亡形态;流式细胞仪检测结果表明在低剂量N-Ag作用下食道癌细胞EC109部分凋亡,且随着