Abstract Heteroleptic ruthenium(II) bioflavonoid complexes of quercetin, morin, chrysin, and 3-hydroxyflavone were prepared and their interaction with CT DNA and BSA along with antioxidant and in vitro anticancer and antimicrobial activities was investigated. The formulation and characterization of complexes were achieved through elemental and thermal analysis, mass spectrometry, 1H NMR spectroscopy along with infrared, electronic absorption, and emission spectroscopy as well as square-wave voltammetry, and magnetic and conductivity measurements. Ruthenium(II) is octahedrally coordinated in cationic complex species to two bidentate diimine ligands (2,2′-bipyridine or 1,10-phenanthroline) and one bidentate monobasic flavonoid ligand through 3,4-site of quercetin, morin, and 3-hydroxyflavone or 4,5-site of chrysin. Complexes bind CT DNA by intercalation and binding constants comparable to ethidium bromide or 10 times higher. Binding constants of complexes to BSA were several times higher compared to ibuprofen and diazepam, and suggest that the complexes have a strong affinity to BSA. Antioxidant activity tests showed that the complexes are more potent in terms of radical inhibition compared to the parent flavonoids. Cytotoxic testing revealed that the Ru(II) complex of quercetin with 2,2′-bipyridine co-ligand has good selectivity to breast adenocarcinoma, while the complex of 3-hydroxyflavone with 2,2′-bipyridine co-ligand showed strong cytotoxicity toward all tested cell lines with IC50 ∼ 1 μM. All complexes showed moderate activity toward Acinetobacter baumannii, while the Ru(II) complex of 3-hydroxyflavone with 2,2′-bipyridine showed excellent activity toward MRSA and Candida albicans.

ABSTRACT Here is the report on the interaction of ruthenium(III) species with DNA in aqueous solution at pH 7.42 by Fourier transformed infrared difference spectroscopy. Under the physiological pH and molar ratio [Ruthenium]/[DNA] = 1/80–1/20 direct binding to guanine-N7, adenine-N7, and surprising binding to exocyclic thymine-O2 was found. At low metal concentration no significant shift of the absorption bands was observed, only nonspecific electrostatic binding of ruthenium(III) with negatively charged phosphate groups occurred. The increase of ruthenium(III) concentration caused DNA double helix destabilization and direct binding of the metal cation to guanine-N7 and thymine-O2. At higher ruthenium(III) concentrations denaturation of the DNA helix is evident with no apparent binding of ruthenium(III) to adenine and cytosine. Helix opening allows migration of ruthenium(III) ions from phosphate to available nucleobases (guanine and thymine). No alteration of the sugar phosphate geometry was observed thus confirming that DNA remains in B conformation.

Abstract The binuclear Ru(II) complexes with Schiff bases derived from 5-chlorosalicyladehyde and 2-aminopyridine and its 5-substituted salicylideneimine homologues were tested in vitro against cervical carcinoma (HeLa), metastatic colorectal adenocarcinoma (SW620), lung adenocarcinoma (A549), breast adenocarcinoma (MCF-7), and human lung fibroblast (WI-38) cell lines. All compounds showed strong antiproliferative activity with extremely low IC50 values. The compounds expressed strong activity against gram-positive bacteria, Staphylococcus aureus and Enterococcus faecalis.

ABSTRACT Here is reported for the first time the application of sodium bis[N-2-oxyphenyl-5-bromosalicylideneiminato-ONO]ruthenate(III) as a mediator with multiwalled carbon nanotubes and Nafion at glassy carbon and screen-printed electrodes for the determination of dopamine in the presence of ascorbic acid. Electrochemical studies were performed using cyclic voltammetry, differential pulse voltammetry, and flow injection amperometry. In flow injection mode, the flow rate was 0.4 mL min−1, the injection volume 250 µL, and the operation potential 0.05 V vs. Ag/AgCl. In 0.1M pH 7.5 phosphate buffer, the sensor provided a linear dynamic range up to 50 mg L−1 dopamine with a detection limit of 0.11 ± 0.04 mg L−1. The sensor was used for the determination of dopamine in ampoules of dopamine hydrochloride by cyclic voltammetry, differential pulse voltammetry, and flow injection amperometry.

The binuclear Ru(II) complexes with Schiff bases derived from 5-chlorosalicyladehyde and 2-aminopyridine and its 5-substituted salicylideneimine homologues were tested in vitro against cervical carcinoma (HeLa), metastatic colorectal adenocarcinoma (SW620), lung adenocarcinoma (A549), breast adenocarcinoma (MCF-7), and human lung fibroblast (WI-38) cell lines. All compounds showed strong antiproliferative activity with extremely low IC50 values. The compounds expressed strong activity against gram-positive bacteria, Staphylococcus aureus and Enterococcus faecalis.

Introduction: Treatment of cancer has been subject of great interest. Researchers are continuously searching for new medicines. In this sense, ruthenium complexes have big potential. Some evidences suggest that ruthenium compounds possess anticancer activities. We synthesized two recently published ruthenium(III) complexes with bidentate O,N and tridentate O,O,N Schiff bases derived from 5-substituted salicylaldehyde and aminophenol or anilineare. These compounds showed affinity for binding to the DNA molecule, however, insufficient data are available regarding their possible toxic effects on biological systems.Methods: In the present study we evaluated genotoxic, cytotoxic, and cytostatic effects of Na[RuCl2(L1)2] and Na[Ru(L2)2], using the Allium cepa assay.Results: Different toxic effects were observed depending on the substance, tested concentration, and endpoint measured. In general, the tested compounds significantly lowered the root growth and mitotic index values as compared to the control group. Additionally, a wide range of abnormal mitotic stages, both clastogenic and non-clastogenic were observed in the treated cells. Na[RuCl2(L1)2] significantly increased the frequency of sticky metaphases, chromosome bridges, micronuclei, impaired chromosome segregation, as well as number of apoptotic and necrotic cells over the controls. In contrast, Na[Ru(L2)2] did not show significant evidence of genotoxicity with regard to chromosome aberrations and micronuclei, however, significant differences were detected in the number of apoptotic and necrotic cells when the highest concentration was applied.Conclusions: In this study we demonstrated antiproliferative effects of Na[RuCl2(L1)2] and Na[Ru(L2)2]. At clinical level, these results could be interesting for further studies on anticancer potential of the ruthenium(III) complexes using animal models.

A dinuclear Schiff base RuII complex derived from 5-chlorosalicylaldehyde and 2-aminopyridine was synthesized. The structure of the compound was analyzed by mass spectrometry as well as IR, UV/Vis, and 1H NMR spectroscopy, along with chemical analysis,as well as magnetic, cyclovoltammetric and conductivity measurements. Two RuII atoms are octahedrally coordinated by azomethine and pyridine nitrogen atoms from two tridentate monobasic Schiff bases and bridging phenol oxygen atoms. The formula of the complex is [Ru2L2Cl2(Et2NH)(H2O)] [L = N-(2-pyridyl)-5-chlorosalicylideneimine and Et2NH = isodiethylamine]. The RuII atoms in the dinuclear neutral complex species have different coordination environments, RuN3O2Cl and RuN2O3Cl. Interaction with CT DNA showed moderate hydrophobic binding. The compound demonstrates strong activity against methicillin-resistant Staphylococcus aureus, methicillin-sensitive Staphylococcus aureus, and especially Enterococcus faecalis. Microbiological tests showed significant inhibition of growth and ability to kill pathogens, similar or even improved compared to reference antibiotics vancomycin.

Ruthenium complexes attracted special attention in recent decades due to their anticancer properties. Since a number of Ru(III) complexes with Schiff bases showed moderate activity to bind DNA, antiproliferative effect of a chloro-ruthenium(III) complex which contains two O,N-bidentate Schiff bases derived from 5-chloro-salicylaldehyde was tested against cervical carcinoma, pancreatic carcinoma, hepatocellular carcinoma, metastatic lesions of colorectal adenocarcinoma and nontumoral cells WI38. The complex showed moderate antiproliferative properties in vitro and significant selectivity to SW620 metastatic lesions of colon cancer. Based on the positive research on ruthenium-based anticancer drugs and their generally moderate cytotoxicity in vitro (IC 50 ) compared to platinum drugs which are in use, the titled compound might be a candidate for investigation in vivo , particularly to SW620.

Eight samples of iron slag and two metallic artefacts from two Early Iron Age sites in central Bosnia and Herzegovina, ��olaci and Pod, were analysed using chemical instrumental methods. Atomic absorption spectrometry was applied to determine major (Fe, Al,Ca, Na, Mg, K and Mn) and trace elements (Cr, Cu, Co, Ni and Zn), while gravimetric method and molecular visible spectrometry were applied to determine Si and Ti, respectively. Infrared spectrum of selected samples was recorded during different phases ofanalysis and the results show that the primary ore was hematite. Results also indicate that residents from both sites, which are adjacent, used the same ore source. Low values of Ca, whose compounds are used as flux in later stages of the processing of iron ore, show that the processing of iron at the study sites was in the beginning stage of its development.Based on the obtained results, metallic artefacts found at the site ��olaci probably came from site Pod. Graphical presentation of the content relation ship between the selected metal oxides in the slag was preformed to present differences between samples from two sites. Analysis of trace elements in the analysed slags confirmed that they originate from Early Iron Age.

The interaction of CT DNA by two anionic Ru(III) complexes with N-substituted salicylidenimine ligands was investigated by spectroscopic titration and cyclic voltammetry. The result gives a surprising evidence for intercalation of DNA by the negatively charged complex species containing non typical intercalating ligands with Kb of order 10 M. Na[RuCl2(N-R-5-X-salim)2], where R represents butyl or phenyl and X = H, Cl, were characterized on the basis of elemental analysis, MALDI-TOF mass spectrometry, infrared, UV / visible spectroscopic measurements and cyclic voltammetry. (doi: 10.5562/cca2216)

The Lexicon of Architects, a part of the “Atlas of 20th Century Croatian Architecture”, is an open book: a project gradually expanding, growing, being supplemented, re-edited, translated, as well as involving a wider scope of media in its presentation. This Lexicon is a sort of gist of established methodological approach of the “Atlas of 20th Century Croatian Architecture”, in which the phenomenon of Croatian architecture is being registered in its basic stage and viewed through the prism of authorial architectural approach. In this regard, this book is perceived not only as a resume of past times but also as an initial reference of development of Croatian cultural space. This edition portrays sixty one architects presented in standard alphabetical order. They have been selected from the generation of architects active during the 20th century, born until 1930. In this way, a relevant scope of architectural production from the beginning of the 20th century up to the 1960’s has been covered. Using selection criteria adapted to the Faculty of Architecture syllabus, the architects were chosen primarily as a reminder for its students, while next issues will supplement the analyzed period but also gradually expand the age limit to those architects active in the 19th century as well as to those nearer to the present time. Relevant contributions on every author are uniform, consisting of an “authorial sheet” i.e. four pages. The introductory page places the author in the chronological framework of Croatian architects. In this issue, they are presented within a wider choice of authors, as a hint of future issues of the Lexicon. This list is supplemented by the list of architects, theoreticians and journalist who had, by their writings, created the framework of architectural discipline in Croatia. The following page presents facts on the life and work of the relevant author. They include essential biographical facts on the architect’s schooling, his/her belonging to a certain circle, and influence on the next generations. The choice of works is reduced to the most important ones ; selected buildings belong in the first place to the representative examples of 20th century Croatian architecture, and only secondly they elaborate an author’s architectural oeuvre. Special care has been taken to exact dating, as well as to the exact location of a relevant building, in order to make these facts of use in an eventual tour of buildings as well as in creating one’s personal architectural guide. The last two pages bring eight illustrations, which not always illustrate the textual choice of works. Instead, on the basis of anthological criteria, they try to illustrate the characteristic authorial expression of the architect in question. The page layout is taken over from the digital presentation media, while the material found in this book is the one of the relevant teaching courses. In fact, it’s scope and reproduction is brought here in the same way and content as it is presented in the digitalized course materials of all study grades at the Faculty of Architecture of the University of Zagreb. The book ends with a registry of architects born until 1960, with their exact position in the “Atlas”. The list is based on the alphabetical and chronological criteria defined by the author’s date of birth. The list includes all the architects with their projects and buildings present in Croatia, as well as those Croatian architects who were active in other countries. Architects presented in this lexicon are: Alfred Albini, Vlado Antolic, Bela Auer, Franjo Bahovec, Helen Baldasar, Aladar Baranyai, Vjekoslav Bastl, Hinko Bauer, Miroslav Begovic, Bernardo Bernardi, Zdravko Bregovac, Emil Ciciliani, Frane Cota, Andrija Cicin-Sain, Julije De Luca, Juraj Denzler, Nikola Dobrovic, Aleksandar Dragomanovic, Zoja Dumengjic, Hugo Ehrlich, Igor Emili, Stanko Fabris, Ignjat Fischer, Drago Galic, Marijan Haberle, Lavoslav Horvat, Drago Ibler, Mladen Kauzlaric, Josip Kodl, Viktor Kovacic, Slavko Lowy, Rudolf Lubynski, Boris Magas, Juraj Neidhardt, Zlatko Neumann, Radovan Niksic, Kazimir Ostrogovic, Lovro Perkovic, Bogdan Petrovic, Josip Picman, Stjepan Planic, Vladimir Potocnjak, Zvonimir Požgaj, Ivo Radic, Božidar Rasica, Vjenceslav Richter, Josip Seissel, Egon Steinmann, Zdenko Strižic, Neven Segvic, Edo Sen, Nada Silovic, Vladimir Sterk, Vladimir Turina, Antun Ulrich, Dinko Vesanovic, Ivan Vitic, Mladen Vodicka, Zvonimir Vrkljan, Ernest Weissmann and Ivan Zemljak.

Leksikon arhitekata Atlasa hrvatske arhitekture dvadesetog stoljeca jest otvorena knjiga: projekt koji se postupno dograđuje, raste, dopunjuje, reizdaje, prosiruje jezicne varijante i medije svog pojavljivanja. Leksikon je svojevrstan sažetak metodoloske tradicije "Atlasa arhitekture" kojim se fenomen hrvatske arhitekture u svojem elementarnom stadiju evidentira i sagledava kroz prizmu autorskoga arhitektonskog postupka. U tom smislu ova knjiga nije zamisljena samo kao resume proteklog vremena vec i kao inicijalna referenca gradnji hrvatskoga kulturoloskog prostora. Objavljeno izdanje predstavlja sezdeset i jednog arhitekta raspoređenih uvriježenim leksikonskim abecednim kljucem, a izlucenih iz generacijskog slijeda arhitekata koji su djelovali u dvadesetom stoljecu, zakljucno s trecim desetljecem, odnosno rođenih do 1930. godine. Na taj nacin pokriven je relevantni opseg arhitektonske produkcije od pocetka stoljeca pa sve do sezdesetih godina. Selekcijskim kljucem prilagođenim nastavnom programu izluceni su autori primarno kao memento studentima Arhitektonskog fakulteta, dok ce buduca izdanja dopunjavati obrađeni period, ali i postupno pomicati generacijski limit prema arhitektima koji su djelovali kako u devetnaestom stoljecu, tako i onima bližim danasnjem trenutku. Prilozi o pojedinom autoru svedeni su na "autorski arak" odnosno na cetiri stranice. Uvodna stranica donosi poziciju autora u generacijskom – kronoloskom slijedu hrvatskih arhitekata. U ovom izdanju radi objektivnosti pregleda oni su predstavljeni unutar sireg odabira autora, ujedno i kao najava povecanog opsega buduceg izdanja Leksikona. Lista je dopunjena evidentiranjem i arhitekata, teoreticara i publicista koji su pisanom rijeci profilirali okvire arhitektonske discipline na podrucju Hrvatske. Sljedeca stranica donosi cinjenice o životu i djelu autora. Faktografski prikaz reduciran je na osnovne biografske i podatke o skolovanju, pripadnosti određenom krugu, odnosno utjecaju autora na nadolazece generacije. Izbor iz djela reduciran je na najznacajnije radove ; selekcionirana djela pripadaju primarno antologijskim primjerima hrvatske arhitekture dvadesetog stoljeca, a tek sekundarno elaboriraju autorovo djelo odnosno opus arhitekta. Posebna pažnja posvecena je preciznosti datacije, kao i egzaktnom pozicioniranju lokaliteta pojedinog djela kako bi se građa mogla koristiti pri obilasku građevina in situ, odnosno profiliranju osobnoga arhitektonskog vodica. Zakljucne dvije stranice "autorskog arka" donose osam slikovnih priloga koji nužno ne prate tekstualni izbor iz djela, ali uz navedeni antologijski kriterij pokusavaju ilustrirati i posebnosti autorskog izraza doticnog arhitekta. Prijelom stranica preuzet je iz medija digitalne prezentacije ; građa knjige ujedno je i građa referentnih nastavnih kolegija, odnosno digitalne skriptarnice preddiplomskog, diplomskog te poslijediplomskog studija Arhitektonskog fakulteta Sveucilista u Zagrebu. Na kraju knjige donijet je registar arhitekata koji su egzaktno pozicionirani u evidenciji "Atlasa", a trenutacno su zakljuceni s generacijskim pragom 1960. godine ; popis je definiran abecednim i kronoloskim kljucem s obzirom na godinu rođenja autora. Njime su obuhvaceni svi oni arhitekti kojih su djela projektirana ili izvedena na prostoru Hrvatske, kao i oni hrvatski arhitekti kojih su djela vezana uz prostore drugih sredina. Prezentirani su arhitekti: Alfred Albini , Vlado Antolic, Bela Auer, Franjo Bahovec, Helen Baldasar, Aladar Baranyai, Vjekoslav Bastl, Hinko Bauer, Miroslav Begovic, Bernardo Bernardi, Zdravko Bregovac, Emil Ciciliani, Frane Cota, Andrija Cicin-Sain, Julije De Luca, Juraj Denzler, Nikola Dobrovic, Aleksandar Dragomanovic, Zoja Dumengjic, Hugo Ehrlich, Igor Emili, Stanko Fabris, Ignjat Fischer, Drago Galic, Marijan Haberle, Lavoslav Horvat, Drago Ibler, Mladen Kauzlaric, Josip Kodl, Viktor Kovacic, Slavko Lowy, Rudolf Lubynski, Boris Magas, Juraj Neidhardt, Zlatko Neumann, Radovan Niksic, Kazimir Ostrogovic, Lovro Perkovic, Bogdan Petrovic, Josip Picman, Stjepan Planic, Vladimir Potocnjak, Zvonimir Požgaj, Ivo Radic, Božidar Rasica, Vjenceslav Richter, Josip Seissel, Egon Steinmann, Zdenko Strižic, Neven Segvic, Edo Sen, Nada Silovic, Vladimir Sterk, Vladimir Turina, Antun Ulrich, Dinko Vesanovic, Ivan Vitic, Mladen Vodicka, Zvonimir Vrkljan, Ernest Weissmann, te Ivan Zemljak.