N-Heteroaromatic hydrazones and dihydrazones of dihydrazides carbonic and thiocarbonic acid:characterization, quantum mechanical study and biological activity.

U okviru disertacije, sintetisane su dve serije jedinjenja: N-heteroaromatični hidrazoni i dihidrazoni dihidrazida ugljene (dhO) i tiougljene kiseline (dhS). Jedan od predmeta istraživanja se odnosio na potpunu strukturnu karakterizaciju N-heteroaromatičnih monohidrazona dihidrazida ugljene kiseline (mh-UK) primenom različitih eksperimentalnih metoda i kvantnohemijskih proračuna. Eksperimentalne metode podrazumevaju rendgensku strukturnu analizu (RSA) i FT-IR (infracrvena spektroskopija sa Furijeovom transformacijom), NMR (nuklearna magnetna rezonancija) i UV-Vis spektoskopiju (ultravioletna-vidljiva spektroskopija). Optimizovane geometrije u vakumu izračunate su pomoću B3LYP/6-311++G(d,p) metode. UV-Vis apsorpcioni spektri, elektronski prelazi i veličine intramolekulskog prenosa naelektrisanja (ICT) su proračunom DCT (rastojanje prenosa naelektrisanja) i QCT (količina prenetog naelektrisanja) vrednosti, kao i AIM (analiza raspodele elektronske gustine na atomima u molekulu) analiza intramolekulske vodonične veze u osnovnom stanju za mh-UK dobijeni pomoću vremenski zavisne DFT metode (TD-DFT, teorija funkcionala gustine u zavisnosti od vremena). Primećeno je da se najjači ICT javlja u E obliku 4-piridinil supstituisanih jedinjenja. Analizirani su UV-Vis apsorpcioni spektri u različitim rastvaračima i ispitivan je njihov uticaj na položaj apsorpcionih maksimuma. Takođe, analiziran je uticaj prirode i položaja supstituenata i ˝aza˝ atoma azota u heteroaromatičnom jezgru i supstituenata na azometisnkom atomu ugljenika na apsorpcione spektre. Za kvantitativnu ocenu uticaja rastvarača na apsorpcione maksimume svih jedinjenja, primenjeni su principi LSER analize (linearna korelacija solvatacionih energija) i to Kamlet-Taft-ovog i Catalán-ovog model. Pozitivan znak koeficijenta a za sva jedinjenja osim za ona koja u svojoj strukturi sadrže hinolinski prsten kod kojih su prisutni supstituenti u položaju 8 ukazuje da je hipsohromni (plavi pomak) uzrokovan veličinom elektron-donorskog efekta supstituenta i jačine vodonične veze koja utiče na elektronsku distribuciju ispitivanih molekula. Dobijeni rezultati ukazuju na bolju stabilizaciju osnovnog stanja u odnosu na pobuđeno stanje...In this thesis, two series of N-Heteroaromatic hydrazones and dihydrazones of dihydrazides carbonic (dhO) and thiocarbonic acid (dhS) have been synthesized. One of the subject this research related to combined experimental and theoretical characterization of the synthesized N-Heteroaromatic monocarbohydrazones (mh-UK), Experimental methods include X-ray single-crystal analysis (XRD), as well as FT-IR (Fourier Transform Infrared Spectroscopy), NMR (Nuclear Magnetic Resonance) and UV-Vis (Ultraviolet–Visible) spectroscopy. Optimized geometries in vacuum have been obtained using B3LYP/6-311++G(d,p) model. Theoretical UV-Vis absorbtion spectra calculation and intramolecular charge transfer (ICT) evaluation was defined with the aid of the charge-transfer distance (DCT) and the amount of transferred charge (QCT) calculation as well as AIM (Atoms in Molecules) analysis have been calculated using TD-DFT (Time Dependant - Density Functional Theory) method. It is noticeable that the strongest ICT occurs in 4-pyridyl substituted compounds. The UV-Vis absorption spectra in various solvents were analyzed and their influence on the position of absorption maxima was examined. The effects of the nature and the position of the substituent and ˝aza˝ nitrogen in heteroaromatic ring on UV-Vis spectra in different solvents have been examined, as well as the impact of different substituents on the azomethine carbon. For quantitative evaluation of the solvent effects on the UV-Vis absorption maxima, the principles of the linear solvation energy relationships (LSER) was applied, i.e. models proposed by Kamlet–Taft and Catalán. The positive sign of coefficient a for all compounds, except for quinoline based compounds wherein a substituent is present in position 8, indicates a hypsochromic (blue) shift relative to increased solvent hydrogen-bond donating capability. This suggests better stabilization of the ground state relative to the excited state..

Supplementary data for the article: Božić, A. R.; Bjelogrlić, S. K.; Novaković, I. T.; Filipović, N. R.; Petrović, P. M.; Marinković, A. D.; Todorović, T. R.; Cvijetić, I. N. Antimicrobial Activity of Thiocarbohydrazones: Experimental Studies and Alignment-Independent 3D QSAR Models. ChemistrySelect 2018, 3 (7), 2215–2221. https://doi.org/10.1002/slct.201702691

Supplementary material for: [https://doi.org/10.1002/slct.201702691]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2094

Supplementary data for the article: Božić, A.; Marinković, A.; Bjelogrlić, S.; Todorović, T. R.; Cvijetić, I. N.; Novaković, I.; Muller, C. D.; Filipović, N. R. Quinoline Based Mono- and Bis-(Thio)Carbohydrazones: Synthesis, Anticancer Activity in 2D and 3D Cancer and Cancer Stem Cell Models. RSC Advances 2016, 6 (106), 104763–104781. https://doi.org/10.1039/c6ra23940d

Supplementary material for: [https://doi.org/10.1039/c6ra23940d]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2352

Anthropometric and Physical Performance Profiles of Elite Karate Kumite and Kata Competitors

Karate tournaments consist of two equally important karate disciplines: the kumite and kata competitions. Due to being based both on the distinctive selection of movement techniques and their kinematic and kinetic patterns, we hypothesized that the elite kumite and kata competitors could differ regarding their anthropometric and physical performance profiles. Thirty-one senior male karate competitors of the national karate team (kumite n = 19; kata n = 12) participated in this study. The tests applied included both the assessment of anthropometric (body height, mass and body mass index) and the following physical performance measurements: the adductor and hamstring flexibility (sideward leg splits test), speed and acceleration (20-m sprint test with 10-m acceleration time), explosive power (countermovement and standing triple jump), agility ("T"- test) and aerobic endurance (20-m multistage shuttle run test). The kumite competitors revealed a larger body size through body height (p = 0.01) and mass (p = 0.03), while the differences in body composition were non-significant. The kumite competitors also demonstrated higher acceleration (p = 0.03) and explosive power (standing triple jump; p = 0.03). A 6-7 degrees higher flexibility of the kata competitors remained somewhat below the level of significance (p = 0.09). The findings could be interpreted by the distinctive differences in the movement techniques. Specifically, a higher explosive power could be beneficial for kumite, while both a smaller stature and higher flexibility (particularly of the lower extremity) could be important for the exceptionally low postures of the kata competitors. Although further elucidation is apparently needed, the obtained finding could be of importance for both the early selection and training of karate competitors

Supplementary data for the article: Božić, A. R.; Bjelogrlić, S. K.; Novaković, I. T.; Filipović, N. R.; Petrović, P. M.; Marinković, A. D.; Todorović, T. R.; Cvijetić, I. N. Antimicrobial Activity of Thiocarbohydrazones: Experimental Studies and Alignment-Independent 3D QSAR Models. ChemistrySelect 2018, 3 (7), 2215–2221. https://doi.org/10.1002/slct.201702691

Supplementary material for: [https://doi.org/10.1002/slct.201702691]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2094

Supplementary material for the article: Milošević, M. D.; Prlainović, N. Ž.; Milčić, M.; Nikolić, V.; Božić, A.; Bigović, M.; Marinković, A. D. Solvent, Structural, Quantum Chemical Study and Antioxidative Activity of Symmetrical 1-Methyl-2,6-Bis[2-(Substituted Phenyl)Ethenyl]Pyridinium Iodides. Journal of the Iranian Chemical Society 2018, 15 (11), 2483–2501. https://doi.org/10.1007/s13738-018-1437-5

Supplementary material for: [https://doi.org/10.1007/s13738-018-1437-5]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2216

Supplementary data for the article: Božić, A.; Marinković, A.; Bjelogrlić, S.; Todorović, T. R.; Cvijetić, I. N.; Novaković, I.; Muller, C. D.; Filipović, N. R. Quinoline Based Mono- and Bis-(Thio)Carbohydrazones: Synthesis, Anticancer Activity in 2D and 3D Cancer and Cancer Stem Cell Models. RSC Advances 2016, 6 (106), 104763–104781. https://doi.org/10.1039/c6ra23940d

Supplementary material for: [https://doi.org/10.1039/c6ra23940d]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2352

Supplementary data for article: Božić, A. R.; Filipović, N. R.; Verbić, T.; Milčić, M. K.; Todorović, T.; Cvijetić, I.; Klisurić, O.; Radišić, M.; Marinković, A. A Detailed Experimental and Computational Study of Monocarbohydrazones. Arabian Journal of Chemistry 2020. https://doi.org/10.1016/j.arabjc.2017.08.010

Supplementary material for: [https://www.sciencedirect.com/science/article/pii/S1878535217301661?via%3Dihub]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/318

N-Heteroaromatic hydrazones and dihydrazones of dihydrazides carbonic and thiocarbonic acid:characterization, quantum mechanical study and biological activity.

U okviru disertacije, sintetisane su dve serije jedinjenja: N-heteroaromatični hidrazoni i dihidrazoni dihidrazida ugljene (dhO) i tiougljene kiseline (dhS). Jedan od predmeta istraživanja se odnosio na potpunu strukturnu karakterizaciju N-heteroaromatičnih monohidrazona dihidrazida ugljene kiseline (mh-UK) primenom različitih eksperimentalnih metoda i kvantnohemijskih proračuna. Eksperimentalne metode podrazumevaju rendgensku strukturnu analizu (RSA) i FT-IR (infracrvena spektroskopija sa Furijeovom transformacijom), NMR (nuklearna magnetna rezonancija) i UV-Vis spektoskopiju (ultravioletna-vidljiva spektroskopija). Optimizovane geometrije u vakumu izračunate su pomoću B3LYP/6-311++G(d,p) metode. UV-Vis apsorpcioni spektri, elektronski prelazi i veličine intramolekulskog prenosa naelektrisanja (ICT) su proračunom DCT (rastojanje prenosa naelektrisanja) i QCT (količina prenetog naelektrisanja) vrednosti, kao i AIM (analiza raspodele elektronske gustine na atomima u molekulu) analiza intramolekulske vodonične veze u osnovnom stanju za mh-UK dobijeni pomoću vremenski zavisne DFT metode (TD-DFT, teorija funkcionala gustine u zavisnosti od vremena). Primećeno je da se najjači ICT javlja u E obliku 4-piridinil supstituisanih jedinjenja. Analizirani su UV-Vis apsorpcioni spektri u različitim rastvaračima i ispitivan je njihov uticaj na položaj apsorpcionih maksimuma. Takođe, analiziran je uticaj prirode i položaja supstituenata i ˝aza˝ atoma azota u heteroaromatičnom jezgru i supstituenata na azometisnkom atomu ugljenika na apsorpcione spektre. Za kvantitativnu ocenu uticaja rastvarača na apsorpcione maksimume svih jedinjenja, primenjeni su principi LSER analize (linearna korelacija solvatacionih energija) i to Kamlet-Taft-ovog i Catalán-ovog model. Pozitivan znak koeficijenta a za sva jedinjenja osim za ona koja u svojoj strukturi sadrže hinolinski prsten kod kojih su prisutni supstituenti u položaju 8 ukazuje da je hipsohromni (plavi pomak) uzrokovan veličinom elektron-donorskog efekta supstituenta i jačine vodonične veze koja utiče na elektronsku distribuciju ispitivanih molekula. Dobijeni rezultati ukazuju na bolju stabilizaciju osnovnog stanja u odnosu na pobuđeno stanje...In this thesis, two series of N-Heteroaromatic hydrazones and dihydrazones of dihydrazides carbonic (dhO) and thiocarbonic acid (dhS) have been synthesized. One of the subject this research related to combined experimental and theoretical characterization of the synthesized N-Heteroaromatic monocarbohydrazones (mh-UK), Experimental methods include X-ray single-crystal analysis (XRD), as well as FT-IR (Fourier Transform Infrared Spectroscopy), NMR (Nuclear Magnetic Resonance) and UV-Vis (Ultraviolet–Visible) spectroscopy. Optimized geometries in vacuum have been obtained using B3LYP/6-311++G(d,p) model. Theoretical UV-Vis absorbtion spectra calculation and intramolecular charge transfer (ICT) evaluation was defined with the aid of the charge-transfer distance (DCT) and the amount of transferred charge (QCT) calculation as well as AIM (Atoms in Molecules) analysis have been calculated using TD-DFT (Time Dependant - Density Functional Theory) method. It is noticeable that the strongest ICT occurs in 4-pyridyl substituted compounds. The UV-Vis absorption spectra in various solvents were analyzed and their influence on the position of absorption maxima was examined. The effects of the nature and the position of the substituent and ˝aza˝ nitrogen in heteroaromatic ring on UV-Vis spectra in different solvents have been examined, as well as the impact of different substituents on the azomethine carbon. For quantitative evaluation of the solvent effects on the UV-Vis absorption maxima, the principles of the linear solvation energy relationships (LSER) was applied, i.e. models proposed by Kamlet–Taft and Catalán. The positive sign of coefficient a for all compounds, except for quinoline based compounds wherein a substituent is present in position 8, indicates a hypsochromic (blue) shift relative to increased solvent hydrogen-bond donating capability. This suggests better stabilization of the ground state relative to the excited state..

Synthesis, antioxidant and antimicrobial activity of carbohydrazones

Fourteen mono- and bis-carbohydrazone ligands have been synthesized and characterized. Antioxidant activity of the substances was investigated together with possible (E)/(Z) isomerization, and explained on the most active antioxidant compound 4 in various dimethyl sulphoxide-water mixtures. The addition of water to the system was involved in the formation of hydrated molecules which was confirmed in NMR after the addition of D2O. The ligands were tested in vitro against Gram-positive and Gram-negative bacteria and fungi, and their activity was discussed in relation to the structure of investigated carbohydrazone