2. Articole

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Nickel (II) Complexes with Pentane-2,4-dione Bis(4-allylthiosemicarbazone) [Articol]
(2020) Gulea, Aurelian; Graur, Vasilii; Ciumacov, Iurie; Petrenko, Peter; Garbuz, Olga; Țapcov, Victor; Gudumac, Valentin
Reaction of pentane-2,4-dione with N-(prop-2-en-1-yl)hydrazinecarbothioamide at a 1: 2 molar ratio in ethanol resulted in the formation of a pyrazole derivative. The latter reacted with nickel perchlorate at a 1: 1 molar ratio to form the nickel complex with pentane-2,4-dione bis(4-allylthiosemicarbazone). The same type of nickel complex was obtained as a result of N-(prop-2-en-1-yl)hydrazinecarbothioamide reaction with pentane-2,4-dione and nickel nitrate at a 2: 1: 1 molar ratio. Antimicrobial, antifungal, antioxidant, and anticancer activities of the obtained compounds were studied.
Novel 2-formylpyridine 4-allyl-S-methylisothiosemicarbazone and Zn(II), Cu(II), Ni(II) and Co(III) complexes: Synthesis, characterization, crystal structure, antioxidant, antimicrobial and antiproliferative activity [Articol]
(2019) Balan, Greta; Usataia, Irina; Graur, Vasilii; Ciumacov, Iurie; Petrenko, Peter; Gudumac, Valentin; Gulea, Aurelian; Pahonțu, Elena; Burduniuc, Olga
New zinc (II), copper (II), nickel (II) and cobalt (III) complexes, [Zn (HL)2]I2 (1), [Cu (HL)Cl2] (2), [Cu (HL)Br2] (3), [Cu (HL)(H2O)2](ClO4)2 (4), [Ni (HL)2]I2·H2O (5), [Co(L)2]Cl (6), [Co(L)2]NO3 (7), [Co(L)2]I·[Co(L)2](I3) (8) were obtained with 2-formylpyridine 4-allyl-S-methylisothiosemicarbazone (HL). The isothiosemicarbazone ligand was characterized by NMR (1H and 13C), IR spectroscopy and X-ray diffraction. All the complexes were characterized by elemental analysis, IR, UV–Vis, ESI-MS spectroscopy, molar conductivity, magnetic susceptibility measurements. X-ray diffraction analysis on the monocrystal and powder elucidated the structure of the complexes 1, 5, 7 and 8. The ligand and the complexes were tested for their antioxidant and antimicrobial activity against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae and Candida albicans. Also, the antiproliferative properties of these compounds on human leukemia HL-60, human cervical epithelial HeLa, human epithelial pancreatic adenocarcinoma BxPC-3, human muscle rhabdomyosarcoma spindle, large multinucleated RD cells and normal MDCK cells have been investigated. The nickel complex 5 and cobalt complexes 6, 7 showed promising antiproliferative activity and low toxicity.
Synthesis, characterization, crystal structure of novel Cu (II), Co (III), Fe (III) and Cr (III) complexes with 2-hydroxybenzaldehyde-4-allyl-S-methylisothiosemicarbazone: Antimicrobial, antioxidant and in vitro antiproliferative activity [Articol]
(2018) Pahonțu, Elena; Usataia, Irina; Graur, Vasilii; Ciumacov, Iurie; Petrenko, Peter; Gudumac, Valentin; Gulea, Aurelian
2-Hydroxybenzaldehyde-4-allyl-S-methylisothiosemicarbazone and Cu (II), Co (III), Fe (III) and Cr (III) complexes were synthesized and characterized. The new obtained compounds were investigated by elemental analysis, magnetic susceptibility measurements, molar electric conductivity, IR, 1H NMR, 13C NMR, UV–Vis spectroscopy. In addition, the structure of the ligand and six complexes has been determined by single-crystal X-ray diffraction analysis. The Cu atom in complex 3 is penta-coordinated in a distorted square–pyramidal coordination geometry, while the metals in complexes 5–9 are in a distorted octahedral environment. For all compounds the antimicrobial activity was studied on a series of standard strains, such as Staphylococcus aureus, Escherichia coli, Enterococcus faecalis, Salmonella abony and Candida albicans. The in vitro antiproliferative activity of the ligand and complexes was screened on human leukemia HL-60 cells, human cervical epithelial HeLa cells, human epithelial pancreatic adenocarcinoma BxPC-3 cells, human muscle rhabdomyosarcoma spindle and large multinucleated RD cells. The primary screening on a wider series of cancer cells showed that copper coordination compound 2 manifests high activity towards HeLa, BxPC-3 and RD cancer cells, which is three–six times higher than the activity of doxorubicin. The selectivity index that is the ratio between the IC50 value for the normal MDCK cells and IC50 values for the cancer cells varies in the range 2.44–21.17. This index is 5.5–11 times higher for the copper coordination compound 2 than for the doxorubicin. Cr (III), Fe (III) and Co (III) coordination compounds 6–9 manifest high antioxidant activity towards ABTS•+ that exceeds 47–67 times the activity of Trolox.
Metodă nouă de apreciere a toxicităţii substanţelor chimice [Articol]
(Imprimt Plus, 2018-09-21) Toderaș, Ion; Gulea, Aurelian; Gudumac, Valentin; Roșcov, Elena; Garbuz, Olga
We developed a new invention that relates to method for assessing the toxicity of chemical substances.The method of the invention includes the preparation of the culture of Paramecium caudatum, adding to the samples investigated to test chemicals in various concentrations, incubating the sample to be studied and control the addition of colourant 3-amino-7-dimethylamino-2-methylphenazine hydrochloride, incubation with subsequent addition of solution of formalin, centrifuging the sample, removing the supernatant, adding the solution of hydroxide of sodium, determine the absorbance using a spectrophotometer, followed by calculating the percentage of paramecii viability and determine the lethal concentration (LC50) at the same time as the value of the concentration LC50 is small, the toxicity of the tested substance is higher.
Expresia enzimelor glutationice în țesutul splenic este influențată de derivații tiosemicarbazidei [Articol]
(2021) Andronache, Lilia; Pantea, Valeriana; Gulea, Aurelian; Șveț, Ina; Ghindă, Sergiu; Privalova, Elena; Smeșnoi, Valentina; Gudumac, Valentin
Administrarea unor baze heterociclice Schiff noi și complexelor lor cu cuprul (II), derivați ai tiosemicarbazidei induce influenţe variate asupra activității enzimelor glutation-dependente în țesutul splenic. Este evidentă acţiunea selectivă a compușilor studiați asupra expresării enzimelor glutationice care se manifestă prin tendinţă de diminuare nesemnificativă a glutationreductazei (GR) și glutationperoxidazei (GPO), creșterea neimportantă a glutation-S-transferazei (GST) și depresia marcată a nivelului glutaredoxinei. Sporul leger al GST la acțiunea compușilor studiați poate fi considerată drept o reacție de protecție orientată să stagneze intensitatea proceselor peroxidice și să susțină activitatea ciclului glutationic, iar diminuarea enzimoactivității glutaredoxinei denotă efectul lor antiproliferativ, citostatic. Sunt necesare studii suplimentare pentru a evalua mecanismele de acțiune ale compușilor cercetați asupra activității enzimelor glutation-dependente în alte biosisteme și experimente pe animale pentru a aprecia importanța practică a rezultatelor obținute.
Micromolecular inhibitors of superoxide radicals [Articol]
(2021) Andronache, Lilia; Pantea, Valeriana; Gulea, Aurelian; Șveț, Inna; Graur, Vasilii; Matcovschi, Valerii; Gamaniuc, Marina; Gudumac, Valentin
Background: Currently, there is a growing interest in new copper (Cu2+) heterocyclic coordination compounds (CC), isothiosemicarbazide derivates, which demonstrated multiple beneficial properties, but their effect on reactions with free radicals such as the superoxide radical has not been investigated. Material and methods: The action of new micromolecular complexes of copper (Cu2+) chloride and bromide with methyl n- (prop-2-en-1-yl) -2- (pyridin2-ylmethylidene) hydrazine carbimidothioate on capturing activity of the superoxide radical was determined by the spectrophotometric method in vitro experiments. Results: It was established that the micromolecular complexes of copper (II) chloride and bromide with methyl n-(prop-2-en-1-yl)-2-(pyridin-2ylmethylidene) hydrazine carbimidothioate have been found to possess strong superoxide radical inhibitor properties when interacting with a superoxide radical. In addition to this, the IC50 of the studied compounds depends on the nature of the acid-ligand in the internal sphere of the complex and increases in the following sequence: Cl-–Br-. Conclusions: The established property of mentioned compounds is new, because their use as micromolecular inhibitors of superoxide radicals has not been described so far. The synthesized CC expand the arsenal of superoxide radical inhibitors with high biological activity. Their possible significance for the development of new treatment strategies for diseases associated with the overproduction of superoxide radicals is discussed.
Thiol-disulfide metabolism in kidney tissue at the administration of some copper coordination compounds [Articol]
(2020) Sardari, Veronica; Pantea, Valeriana; Gulea, Aurelian; Tagadiuc, Olga; Andronache, Lilia; Șveț, Inna; Țapcov, Victor; Gudumac, Valentin
Thiol-disulfide metabolism is essential for normal function of the organism. Thus the interest of the scientists in this area of research continues to grow. Material and methods: Copper coordination compounds (CCC), derivatives of thiosemicarbaside (CMD-4, CMJ-33, CMT-67), action on thiol-disulfide metabolism in the healthy Ratta albicans kidneys were studied. The animals were divided in 6 groups of 7 rats each. The control group included healthy rats which were injected i/m physiological solution 3 times a week, for 30 days. The rats from groups 2-6 have got 3 times a week, for 30 days, i/m injections of CCC. The activity of following thiol-disulfide metabolism enzymes in the renal supernatant has been measured: glutathion-reductase (GR), glutathion-peroxidase (GPO), glutathion-S-transferase (G-S-T), γ-glutamyl transpeptidase (γ-GTP), glutaredoxin (Grx), as well the amount of the protein SH-groups and of the total glutathione, reduced glutathione (GSH) and oxidized glutathione (GSSG) in renal tissue. Results: The compounds exhibit different actions: CMT-67 in the dose of 0.1 μM/kg influenced the activity of the glutathione metabolism enzymes – activated γ-glutamyl transpeptidase (γ-GTP) and glutaredoxine (Grx) and inhibited glutathione reductase (GR), while CMD-4 in doses of 0.1 μM/kg and 1.0 μM/kg and CMJ-33 in the dose of 1.0 μM/kg significantly diminished the reduced glutathione (GSH) level and increased the amount of the oxidised one (GSSG). Conclusions: Selective action of the copper coordination copounds established by this study opens new possibilities of their usage in the therapy of kidney diseases.
Coordination compound as inhibitor of superoxid radical [Articol]
(2019) Garbuz, Olga; Pantea, Valeria; Usataia, Irina; Graur, Vasilii; Țapcov, Victor; Sardari, Veronica; Tagadiuc, Olga; Gudumac, Valentin; Gulea, Aurelian
A fost obținut un nou compus coordinativ biologic activ, nitratul de cupru [2 - ({2 [(ethylsulfanyl) (prop-2-en-1-yl) carbononoimidooyl] -hydrazinylidene} methyl) phenolate], care face parte din clasa isotiosemicarbazidelor metalelor de tranziție.S-a stabilit că acesta exercită proprietăți anti radicalice performante la acțiunea moleculei organice cu radicalul superoxidic. Datorită acestei poroprietăți compusul obținut poate avea o potențială aplicare in medicină in calitate de inhibitor al radicalilor superoxidici in corpul uman, care poate duce la prevenirea deteriorării tesutului cellular, aterosclerozii si carcinogenezei.Compusul coordinativ sintetizat extinde arsenalul inhibitorilor de radicali superoxidici cu activitate biologică importanta.
Influence of copper coordination compounds and cyanobacterian remedy BioR on bone collagen and hydroxyproline concentrations (ontogenetic view) [Articol]
(Elan-Poligraf, 2011-07-07) Tagadiuc, Olga; Gulea, Aurelian; Rudic, Valeriu; Gudumac, Valentin
The aim of our research was to assess the influence of copper coordination compounds CMT-28 and CMT-67 and cyanobacterian remedy BioR on bone collagen and hydroxyproline (HYP) concentrations at different stages of postnatal ontogenesis in normal physiological conditions and experimental osteopathy (EO). The survey was conducted on a sample of 301 white laboratory rats of both sexes, which were divided depending on their stage of postnatal ontogenetic development and experimental model: control; animal with experimental osteopathy (EO); animals with EO+CMT-28 1 mg/kg body weight; animals with EO+CMT-67 1 mg/kg body weight; animals with EO+BioR 1mg/kg body weight; animals with EO+BioR 2 mg/kg body weight; animals with EO+CMT-28+BioR (1 mg/kg body weight each); animals with EO+BioR+CMT-67 (1 mg/kg body weight each). In physiological conditions the ontogenetic modifications of the bone collagen and HYP content are statistically conclusive and of the same orientation, the maximum concentration was identified in adult animals and the minimum at advanced stages of postnatal ontogenesis regardless of sex. Experimental osteopathy is characterized by age and sex dependent changes of the collagen and hydroxyproline concentrations in bone, the most significant changes being revealed in young females. Copper coordination compounds, BioR and their combinations increase the turnover of the collagen in bone in EO that is accompanied by decrease of collagen and increase of the HYP concentration that is probably a compensatory mechanism oriented to the replacement of the damaged collagen and the restoration of its normal nanostructure with the recovery of the bone.
In vitro antiproliferative activity and antioxidant capacity of new organometallic coordination compounds, results correlation analysis [Articol]
(2016) Gulea, Aurelian; Gudumac, Valentin; Garbuz, Olga; Andronache, Lilia
A fost examinată și testată capacitatea inhibitorilor organometalici activi CMJ-33, CMSA-4, de a induce apoptoza în celulele epiteliale de carcinom de col uterin linia HeLa. Viabilitatea celulelor canceroase a fost determinată prin testul Alamar Blue fiind folosit un indicator redox – resazurin. S-a depistat activitate antitumorală mai mare a substanțelor testate decât la cea luată în calitate de etalon: - doxorubicina (DOXO). În scopul de a detecta eventuala prezenţă a efectelor adverse concomitente legate cu proprietățile pro-oxidante ale compușilor coordinativi, a fost folosită metoda cantitativă ORAC (Oxygen Radical Absorption Capacity). Rezultatele au demonstrat că substanțele testate CMT-67 şi CMSA-4 posedă activitate antioxidantă mai mare decât Trolox și DOXO. În această lucrare, noi constatăm prezența unei corelații pozitive semnificative (coeficient de corelație - 0,98) între efectele anti-proliferative și anti-oxidante pentru compuşii CMT-67, CMSA-4 și DOXO.

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