Synthesis, Characterization, and In Vitro Cytotoxic Activities of Benzaldehyde Thiosemicarbazone Derivatives and Their Palladium (II) and Platinum (II) Complexes against Various Human Tumor Cell Lines

The palladium (II) bis-chelate Pd (L1−3)2 and platinum (II) tetranuclear Pt4(L4)4 complexes of benzaldehyde thiosemicarbazone derivatives have been synthesized, and characterized by elemental analysis and IR, FAB(+)-mass and NMR (1H, 13C) spectroscopy. The complex Pd(L2)2 [HL2 = m-CN-benzaldehyde thiosemicarbazone] shows a square-planar geometry with two deprotonated ligands (L) coordinated to PdII through the nitrogen and sulphur atoms in a transarrangement, while the complex Pt4(L4)4 [HL4 = 4-phenyl-1-benzaldehyde thiosemicarbazone] has a tetranuclear geometry with four tridentate ligands coordinated to four PtII ions through the carbon (aromatic ring), nitrogen, and sulphur atoms where the ligands are deprotonated at the NH group. The in vitro antitumor activity of the ligands and their complexes was determined against different human tumor cell lines, which revealed that the palladium (II) and platinum (II) complexes are more cytotoxic than their ligands with IC50 values at the range of 0.07–3.67 μM. The tetranuclear complex Pt4(L4)4, with the phenyl group in the terminal amine of the ligand, showed higher antiproliferative activity (CI50 = 0.07–0.12 μM) than the other tested palladium (II) complexes

Synthesis, Characterization And Antitumor Activity Of Copper(II) Complexes, [CuL2] [HL1-3=N,N-Diethyl-N'-(R-Benzoyl)Thiourea (R=H, o-Cl and p-NO2)]

The copper (II) complexes (CuL2) were prepared by reaction of Cu(CH3COO)2 with the corresponding derivatives of acylthioureas in a Cu:HL molar ratio of 1:2. Acylthiourea ligands, N,N-diethyl-N'-(R-benzoyl) thiourea (HL1-3) [R=H, o-Cl and p-NO2] were synthesized in high yield (78-83%) and characterized by elemental analysis, infrared spectroscopy, 1H and 13C NMR spectroscopy. The complexes CuL2 were characterized by elemental analysis, IR, FAB(+)-MS, magnetic susceptibility measurements, EPR and cyclic voltammetry. The crystal structure of the complex Cu(L2)2 shows a nearly square-planar geometry with two deprotonated ligands (L) coordinated to CuII through the oxygen and sulfur atoms in a cis arrangement. The antitumor activity of the copper(II) complexes with acylthiourea ligands was evaluated in vitro against the mouse mammary adenocarcinoma TA3 cell line. These complexes exhibited much higher cytotoxic activity (IC50 values in the range of 3.9-6.9 μM) than their corresponding ligands (40-240 μM), which indicates that the coordination of the chelate ligands around the CuII enhances the antitumor activity and, furthermore, this result confirmed that the participation of the nitro and chloro substituent groups in the complex activities is slightly relevant. The high accumulation of the complexes Cu(L2)2 and Cu(L3)2 in TA3 tumor cells and the much faster binding to cellular DNA than Cu(L1)2 are consistent with the in vitro cytotoxic activities found for these copper complexes

Novel Thiosemicarbazone Derivatives from Furan-2-Carbaldehyde: Synthesis, Characterization, Crystal Structures, and Antibacterial, Antifungal, Antioxidant, and Antitumor Activities

Ten new thiosemicarbazone derivatives, furan-2-carbaldehyde thiosemicarbazone (1), 3-methyl-furan-2-carbaldehyde thiosemicarbazone (2), 5-hydroxymethyl-furan-2-carbaldehyde thiosemicarbazone (3), 5-trifluoromethyl-furan-2-carbaldehyde thiosemicarbazone (4), 5-nitro-furan-2-carbaldehyde thiosemicarbazone (5), 5-phenyl-furan-2-carbaldehyde thiosemicarbazone (6), 5-(2-fluorophenyl)-furan-2-carbaldehyde thiosemicarbazone (7), 5-(4-methoxyphenyl)-furan-2-carbaldehyde thiosemicarbazone (8), 5-(1-naphthyl)-furan-2-carbaldehyde thiosemicarbazone (9), and 5-(1H-Pyrazol-5-yl)-furan-2-carbaldehyde thiosemicarbazone (10) were synthesized by condensing thiosemicarbazide with the respective furan-2-carbaldehyde in methanol. The prepared compounds were characterized by spectroscopic studies (FT-IR and NMR) and electrospray mass spectrometry. The molecular structures of 2, 6, 7, and 8 have also been determined by X-ray crystallography. Compounds 2, 6, and 7 crystallize in the E conformation about the N1-C6, N1-C11, and N1-C11 bonds, respectively, while 8 adopts the Z conformation about the N1-C12 bond with the presence of an intramolecular N2-H.O2 hydrogen bond. All prepared thiosemicarbazone derivatives were evaluated for their in vitro antibacterial, antifungal, and antitumor activities against Staphylococcus aureus strains, Candida albicans/Candida tropicalis fungi, and seven human tumor cell lines (HuTu80, H460, DU145, M-14, HT-29, MCF-7, and LNCaP), respectively. The antioxidant activity was also studied by the DPPH assay. Compound 5 exhibited significant antibacterial activity against Staphylococcus aureus ATCC700699 (MIC = 1 µg/mL) compared to the nitrofurantoin and gentamicin reference drugs (MIC = 1-25 and 10->100 µg/mL, respectively). Compound 4 was ten times less active than amphotericin B (MIC = 5 µg/mL) against Candida albicans (ATCC90028 and ATCC10231), while 1 exhibited a moderate effect of scavenging of DPPH radical (IC50 = 40.9 µg/mL) in comparison to ascorbic acid reference compound (IC50 = 22.0 µg/mL). Among all the studied thiosemicarbazones, 5 showed a higher cytotoxic activity (IC50 = 13.36-27.73 µ¿) in relation to the other tested compounds (IC50 = 34.84 - >372.34 µ¿) against all tested cell lines, except the LNCaP cell line, exhibiting its highest antiproliferative activity (IC50 = 13.36 µ¿) on the HuTu80 cell line. Besides, 8 and 9 exhibited high antitumor activity (IC50 = 13.31 and 7.69 µ¿, respectively) against the LNCaP cells.Revisión por pare

Synthesis, Characterization and Antitumor Activity of cis-bis(acylthioureato) platinum(II) Complexes, cis-[PtL2] [HL1=N,N-Diphenyl-N'-Benzoylthiourea or HL2=N,N-diphenyl-N'-(p-nitrobenzoyl)thiourea]

A low-molecular weight chromium-containing fraction of the material resulting from dichromate reduction by bovine liver homogenate was investigated by NMR and ES-MS. The ES-MS spectrum showed a readily detectable peak at m/z 786.1. The same molecular weight reasonably agreed with the relatively low diffusion coefficient measured by NMR-DOSY experiments on the main species observed in the 1H NMR spectrum. At least two downfield shifted and broad paramagnetic signals were apparent in the 1H NMR spectrum. Temperature dependence of chemical shift was exploited in order to estimate the diamagnetic shift of the signals in the diamagnetic region of the spectrum. 2D TOCSY, NOESY, COSY and 1H-13C HMQC spectra revealed the presence of aromatic protons (which were assigned as His residues), Gly and some other short chain amino-acids. Combinations of the molecular masses of such components together with acetate (which is present in the solution) and chromium atoms allowed a tentative proposal of a model for the compound

Models to predict the magnetic properties of single- and multiple-bridged phosphate Cu-II systems: a theoretical DFT insight

Copper(II) phosphate bridged compounds have been studied by DFT methods in order to gain a better understanding of the magnetic exchange interactions through 1,1 and 1,3-bridges, which vary with the bonding modes of the ligand. In many cases phosphate is only one among several bridging ligands making it difficult to identify the predominant exchange pathway. This work proposes a graphical analysis, based on the unrestricted corresponding orbitals (UCO), and the derived 'magnetic orbitals' to identify the predominant exchange pathway. Models for the 1,1- and 1,3-bridging modes allow establishing the angle or dihedral dependence of the J values. For the 1,1-bridging mode the theta Cu-O-Cu angle was used. For the 1,3-phosphate the correlation was established with a D-P-O-i-Cu-i dihedral angle (tau) where D is a dummy atom. Using models with different D-P-O-i-Cu-i dihedral angles a predictive scheme was generated. Eleven copper(II) phosphate bridged structures were used to validate the proposed model. The study has shown that antiferromagnetic exchange interactions are primarily produced by phosphate bridges due to the possibility of this ligand that always enables a degree of overlap between the magnetic orbitals

Synthesis, characterization, and in vitro cytotoxic activities of benzaldehyde thiosemicarbazone derivatives and their palladium(II) and platinum(II) complexes against various human tumor cell lines

The palladium (II) bis-chelate Pd (L 1 - 3) 2 and platinum (II) tetranuclear Pt 4 (L 4) 4 complexes of benzaldehyde thiosemicarbazone derivatives have been synthesized, and characterized by elemental analysis and IR, FAB (+) -mass and NMR (1 H, 13 C) spectroscopy. The complex Pd (L 2) 2 [H L 2 = m -CN-benzaldehyde thiosemicarbazone] shows a square-planar geometry with two deprotonated ligands (L) coordinated to Pd II through the nitrogen and sulphur atoms in a transarrangement, while the complex Pt 4 (L 4) 4 [H L 4 = 4 -phenyl-1-benzaldehyde thiosemicarbazone] has a tetranuclear geometry with four tridentate ligands coordinated to four Pt II ions through the carbon (aromatic ring), nitrogen, and sulphur atoms where the ligands are deprotonated at the NH group. The in vitro antitumor activity of the ligands and their complexes was determined against different human tumor cell lines, which revealed that the palladium (II) and platinum (II) complexes are more cytotoxic than their ligands with IC 50 values at the range of 0.07-3.67 µM. The tetranuclear complex Pt 4 (L 4) 4, with the phenyl group in the terminal amine of the ligand, showed higher antiproliferative activity (CI 50 = 0.07-0.12 µM) than the other tested palladium (II) complexes

Catena-(bis((1,10-Phenanthroline-N,N')-copper(II)) hydroxy-bis( phosphato)-tris(dioxo-vanadium(v))): a polymorphic phase driven by disorder.

International audienceIn the present paper a copper(II) phosphovanadate is presented and formulated as [Cu6(phen)6(VVO2)6(PO4)6(VVO2HO)3] (1a). This compound was obtained by hydrothermal synthesis and crystallizes in the triclinic group P-1, with a = 10.6290(5), b = 17.4275(8), c = 23.6151(11) Å; α = 92.888(4)°, β = 98.910(4)° and γ = 91.995(4)°. The leitmotif in (1a) is almost identical to some previously reported ones, viz. [Cu(phen)(VVO2)(PO4)]2[VVO2(OH)] (2); [Cu(phen)(VVO2)(PO4)]2[VIVO2(H2O)] (3) except for the fact that the small cells found in (2)-(3) are tripled in (1a). The reasons driving to these differences are subtle, and reside in the way in which the disorder in some vanadate groups takes place, viz., completely at random in (2)-(3) thus leading to a small "average" cell, while keeping some systematics in (1a) thus needing for a larger motif to take account of its repetition scheme in the crystal. The magnetic unit in the structure of (1a) is defined by a dinuclear system of CuII bonded by a μ2,η1-PO4 bridge. A fit of the corresponding magnetic data of (1a) was done, using the van Vleck equation for two S = ½ centres View the MathML source. The parameters obtained by the fit of the experimental data were g = 2.1 and J = −3.5 cm−1

Materiales bioinorgánicos de paladio con compuestos orgánicos derivados de la tiosemicarbazona de actividad antitumoral

El presente trabajo informa acerca de la preparación, caracterización y actividad anti tu moral de nuevos compuestos orgánicos (ligantes) del tipo tiosemicarbazona, RCH=N-NHC(S)-NH2 [R=pirrol-2-carboxaldehído y tiofeno 2-carboxaldehído] y sus complejos me tálicos de paladio(II). El análisis elemental y las técnicas espectroscópicas de infrarrojo y resonancia magnética nuclear de protón y carbono revelan que los ligantes tiosemicarbazonas están desprotonados y se encuentran enlazados al centro metálico a través de dos áto mos de nitrógeno (N) y azufre (S) en una configuración trans

Materiales bioinorgánicos de paladio y cobre con compuestos orgánicos de actividad antitumoral

En el presente trabajo se informa acerca de la preparación y caracterización de los compuestos orgánicos derivados del furaldehído tiosemicarbazona y sus respectivos complejos metálicos de paladio(II) y co bre(II). El análisis elemental y las técnicas espectroscópicas confirman las fórmulas estructurales propuestas para los ligantes orgánicos y sus respectivos complejos de paladio(II) y cobre(II). La actividad biológica in vitro de los ligantes y los complejos metálicos reveló que los complejos de paladio(II), Pd(LF4)2 y Pd(LF5)2 presentan mayor actividad citotóxica in vitro (CI50= 0.28 - 1.23 μM) con respecto a los ligantes frente a diferentes líneas de células tumorales de humano

Materiales bioinorgánicos de paladio y cobre con compuestos orgánicos de actividad antitumoral

En el presente trabajo se informa acerca de la preparación y caracterización de los compuestos orgánicos derivados del furaldehído tiosemicarbazona y sus respectivos complejos metálicos de paladio(II) y co bre(II). El análisis elemental y las técnicas espectroscópicas confirman las fórmulas estructurales propuestas para los ligantes orgánicos y sus respectivos complejos de paladio(II) y cobre(II). La actividad biológica in vitro de los ligantes y los complejos metálicos reveló que los complejos de paladio(II), Pd(LF4)2 y Pd(LF5)2 presentan mayor actividad citotóxica in vitro (CI50= 0.28 - 1.23 μM) con respecto a los ligantes frente a diferentes líneas de células tumorales de humano