Experimental and quantum-chemical studies of quinolone azo dyes and their precusors.

Predmet istraživanja ove doktorske disertacije bila je eksperimentalna i teorijska analiza strukture hinolonskih azo boja i njihovih prekursora. U okviru disertacije, izvršena je sinteza azo boja kod kojih je ulogu kuplujuće komponente imao 4-hidroksi- -2-hinolon, dok je diazo komponenta bila odgovarajući p-supstituisan anilin. Najpre je izvršena sinteza serije N,N’-bisarilmalonamida (prekursora hinolona) čija je detaljna analiza (eksperimentalna i teorijska) dala odgovore u vezi sa geometrijom i reaktivnošću ispitivanih prekursora. Proučavan je uticaj supstituenata fenilnog jezgra, na azo-hidrazon tautomeriju u rastvorima (kod azo boja), kao i na geometriju i reaktivnost prekursora (kod N,N’-bisarilmalonamida). Takođe, proučavan je uticaj i rastvarača na formiranje intra- i intermolekulske vodonične veze kod N,N’-bisarilmalonamida. Izvršena je analiza uticaja rastvarača na apsorpcione spektre ispitivanih jedinjenja primenom linearne korelacije energije solvatacije (LSER) uz korišćenje Kamlet-Taftove (Kamlet-Taft) i Katalanove (Catalán) jednačine. Urađena je i optimizacija geometrije ispitivanih jedinjenja i proučeno je prenošenje elektronskih efekata primenom kvantno-hemijskih proračuna (DFT). Sva jedinjenja sintetisana su prema originalnim ili modifikovanim metodama iz literature. Jedinjenja su okarakterisana temperaturama topljenja, UV-Vis, FT-IR, 1H i 13C NMR spektrima i elementarnom analizom. Na osnovu spektralnih podataka utvrđena je struktura tautomernih oblika boja. UV-Vis apsorpcioni maksimumi određeni su u različitim rastvaračima (spektroskopske čistoće). Uticaj supstituenata na prenošenje elektronskih efekata kod N,N’-bisarilmalonamida ispitan je primenom jednoparametarske i dvoparametarske Hametove (Hammett) jednačine, kao i primenom Svain-Luptonove (Swain-Lupton) jednačine. Rezultati dobijeni UV-spektroskopskim merenjima (kod N,N'-bisarilmalonamida) pokazuju, da na položaj UV-apsorpcionih frekvencija mnogo više utiče prisutni supstituent na fenilnom prstenu, nego svojstva rastvarača. Kamlet-Taft analiza je pokazala da solvatohromizam nastaje najvećim delom zbog dipolarnosti/polarizabilnosti rastvarača. Rezultati dobijeni Hametovom jednačinom ukazuju na postojanje proširene delokalizacije. Kvantno mehanički poračuni ukazuju da u zavisnosti od okolnog medijuma molekuli N,N'-bisarilmalonamida mogu imati različitu geometriju. Rezultati dobijeni FT-IR i UV-Vis analizom hinolonskih boja pokazuju postojanje tautomerije kao i dominantnost hidrazo-keto oblika u odnosu na druge. Uticaj supstituenata na fenilnom jezgru na UV-Vis apsorpcione spektre takođe je veći nego uticaj rastvarača. NBO analize daju jasnu sliku o intramolekulskom prenosu naelektrisanja kod ispitivanih jedinjenja u zavisnosti od prisutnih supstituenata...Subject of this doctoral dissertation is the experimental and theoretical analysis of quinolone azo dyes and their precursors structure. Within the theses, the synthesis of azo dyes in which the role of the coupling components had the 4-hydroxy-2-quinolone while the diazo component was the corresponding p-substituted aniline, was carried out. First the synthesis of a series of N,N'-bisarylmalonamides (precursor) was performed. In-depth analysis (experimental and theoretical) of the prepared amides afforded the answers regarding the geometry and the reactivity of the tested precursors. The impact of the nature of the substituents on the phenyl nucleus, on the azo-hydrazone tautomerism in solution (with azo dyes), as well as the geometry and the reactivity of the precursor (N,N'-bisarilmalonamida) was studied. Also, the influence of solvents on the azo-hydrazone tautomerism of azo dyes as well as the solvent effect on the formation of intra- and intermolecular hydrogen bonds in N,N'-bisarylmalonamides was investigated. The analysis was performed using linear correlation free energy of solvation (LSER) using Kamlet-Taft and Catalan equations. Has been done the optimization of the tested compounds and examined the transmission of electronic effects of the application of quantum-chemical calculations (DFT). All compounds were synthesized according to the original or modified methods from the literature. The compounds were characterized by melting point, UV-Vis, FT-IR, 1H and 13C NMR spectra and elemental analysis. Determination of UV-Vis absorption maximum in a variety of solvents (spectroscopic grade) was carried out using a UV-Vis spectrophotometer. The effect of substituents on the transmission of electronic effects in N,N’-bisarylmalonamides was tested using simple and extended Hammett equations, as well as by Swain-Lupton equation. The results obtained by UV spectroscopic measurements (the N,N'-bisarilmalonamida) shows that the position of a UV absorption frequency much more affects the nature of substituents present on the phenyl ring than the properties of the solvent. Kamlet-Taft analysis showed that solvatochromism occurs mainly due dipolarity/polarizability solvent. Results obtained using the Hammett equation, indicate the existence of extended delocalization. The quantum mechanical calculations indicate that depending on the surrounding medium molecule N,N'-bisarilmalonamida can have various geometry. The results obtained by FT-IR and UV-Vis analysis of quinolone azo dyes indicate the existence of tautomerism and dominance of hydrazo-keto form. The influence of nature of the substituents on the phenyl nucleus in UV-Vis absorption spectra is also higher than the effect of the solvent. NBO analysis results give a clear picture of intramolecular charge transfer of the tested compounds according to the substituents present compounds..

A review of the international early recommendations for departments organization and cancer management priorities during the global COVID-19 pandemic: applicability in low- and middle-income countries.

Coronavirus disease 2019 (COVID-19) is an infectious disease caused by a new virus that has never been identified in humans before. COVID-19 caused at the time of writing of this article, 2.5 million cases of infections in 193 countries with 165,000 deaths, including two-third in Europe. In this context, Oncology Departments of the affected countries had to adapt quickly their health system care and establish new organizations and priorities. Thus, numerous recommendations and therapeutic options have been reported to optimize therapy delivery to patients with chronic disease and cancer. Obviously, while these cancer care recommendations are immediately applicable in Europe, they may not be applicable in certain emerging and low- and middle-income countries (LMICs). In this review, we aimed to summarize these international guidelines in accordance with cancer types, making a synthesis for daily practice to protect patients, staff and tailor anti-cancer therapy delivery taking into account patients/tumour criteria and tools availability. Thus, we will discuss their applicability in the LMICs with different organizations, limited means and different constraints

MUM ENHANCERS are important for seed coat mucilage production and mucilage secretory cell differentiation in Arabidopsis thaliana

Pollination triggers not only embryo development but also the differentiation of the ovule integuments to form a specialized seed coat. The mucilage secretory cells of the Arabidopsis thaliana seed coat undergo a complex differentiation process in which cell growth is followed by the synthesis and secretion of pectinaceous mucilage. A number of genes have been identified affecting mucilage secretory cell differentiation, including MUCILAGE-MODIFIED4 (MUM4). mum4 mutants produce a reduced amount of mucilage and cloning of MUM4 revealed that it encodes a UDP-L-rhamnose synthase that is developmentally up-regulated to provide rhamnose for mucilage pectin synthesis. To identify additional genes acting in mucilage synthesis and secretion, a screen for enhancers of the mum4 phenotype was performed. Eight mum enhancers (men) have been identified, two of which result from defects in known mucilage secretory cell genes (MUM2 and MYB61). Our results show that, in a mum4 background, mutations in MEN1, MEN4, and MEN5 lead to further reductions in mucilage compared to mum4 single mutants, suggesting that they are involved in mucilage synthesis or secretion. Conversely, mutations in MEN2 and MEN6 appear to affect mucilage release rather than quantity. With the exception of men4, whose single mutant exhibits reduced mucilage, none of these genes have a single mutant phenotype, suggesting that they would not have been identified outside the compromised mum4 background

Linkage Mapping of Stem Saccharification Digestibility in Rice

Rice is the staple food of almost half of the world population, and in excess 90% of it is grown and consumed in Asia, but the disposal of rice straw poses a problem for farmers, who often burn it in the fields, causing health and environmental problems. However, with increased focus on the development of sustainable biofuel production, rice straw has been recognized as a potential feedstock for non-food derived biofuel production. Currently, the commercial realization of rice as a biofuel feedstock is constrained by the high cost of industrial saccharification processes needed to release sugar for fermentation. This study is focused on the alteration of lignin content, and cell wall chemotypes and structures, and their effects on the saccharification potential of rice lignocellulosic biomass. A recombinant inbred lines (RILs) population derived from a cross between the lowland rice variety IR1552 and the upland rice variety Azucena with 271 molecular markers for quantitative trait SNP (QTS) analyses was used. After association analysis of 271 markers for saccharification potential, 1 locus and 4 pairs of epistatic loci were found to contribute to the enzymatic digestibility phenotype, and an inverse relationship between reducing sugar and lignin content in these recombinant inbred lines was identified. As a result of QTS analyses, several cell-wall associated candidate genes are proposed that may be useful for marker-assisted breeding and may aid breeders to produce potential high saccharification rice varieties

Diverse aging rates in ectothermic tetrapods provide insights for the evolution of aging and longevity

Comparative studies of mortality in the wild are necessary to understand the evolution of aging; yet, ectothermic tetrapods are underrepresented in this comparative landscape, despite their suitability for testing evolutionary hypotheses. We present a study of aging rates and longevity across wild tetrapod ectotherms, using data from 107 populations (77 species) of nonavian reptiles and amphibians. We test hypotheses of how thermoregulatory mode, environmental temperature, protective phenotypes, and pace of life history contribute to demographic aging. Controlling for phylogeny and body size, ectotherms display a higher diversity of aging rates compared with endotherms and include phylogenetically widespread evidence of negligible aging. Protective phenotypes and life-history strategies further explain macroevolutionary patterns of aging. Analyzing ectothermic tetrapods in a comparative context enhances our understanding of the evolution of aging.Animal science

Experimental and quantum-chemical studies of quinolone azo dyes and their precusors.

Predmet istraživanja ove doktorske disertacije bila je eksperimentalna i teorijska analiza strukture hinolonskih azo boja i njihovih prekursora. U okviru disertacije, izvršena je sinteza azo boja kod kojih je ulogu kuplujuće komponente imao 4-hidroksi- -2-hinolon, dok je diazo komponenta bila odgovarajući p-supstituisan anilin. Najpre je izvršena sinteza serije N,N’-bisarilmalonamida (prekursora hinolona) čija je detaljna analiza (eksperimentalna i teorijska) dala odgovore u vezi sa geometrijom i reaktivnošću ispitivanih prekursora. Proučavan je uticaj supstituenata fenilnog jezgra, na azo-hidrazon tautomeriju u rastvorima (kod azo boja), kao i na geometriju i reaktivnost prekursora (kod N,N’-bisarilmalonamida). Takođe, proučavan je uticaj i rastvarača na formiranje intra- i intermolekulske vodonične veze kod N,N’-bisarilmalonamida. Izvršena je analiza uticaja rastvarača na apsorpcione spektre ispitivanih jedinjenja primenom linearne korelacije energije solvatacije (LSER) uz korišćenje Kamlet-Taftove (Kamlet-Taft) i Katalanove (Catalán) jednačine. Urađena je i optimizacija geometrije ispitivanih jedinjenja i proučeno je prenošenje elektronskih efekata primenom kvantno-hemijskih proračuna (DFT). Sva jedinjenja sintetisana su prema originalnim ili modifikovanim metodama iz literature. Jedinjenja su okarakterisana temperaturama topljenja, UV-Vis, FT-IR, 1H i 13C NMR spektrima i elementarnom analizom. Na osnovu spektralnih podataka utvrđena je struktura tautomernih oblika boja. UV-Vis apsorpcioni maksimumi određeni su u različitim rastvaračima (spektroskopske čistoće). Uticaj supstituenata na prenošenje elektronskih efekata kod N,N’-bisarilmalonamida ispitan je primenom jednoparametarske i dvoparametarske Hametove (Hammett) jednačine, kao i primenom Svain-Luptonove (Swain-Lupton) jednačine. Rezultati dobijeni UV-spektroskopskim merenjima (kod N,N'-bisarilmalonamida) pokazuju, da na položaj UV-apsorpcionih frekvencija mnogo više utiče prisutni supstituent na fenilnom prstenu, nego svojstva rastvarača. Kamlet-Taft analiza je pokazala da solvatohromizam nastaje najvećim delom zbog dipolarnosti/polarizabilnosti rastvarača. Rezultati dobijeni Hametovom jednačinom ukazuju na postojanje proširene delokalizacije. Kvantno mehanički poračuni ukazuju da u zavisnosti od okolnog medijuma molekuli N,N'-bisarilmalonamida mogu imati različitu geometriju. Rezultati dobijeni FT-IR i UV-Vis analizom hinolonskih boja pokazuju postojanje tautomerije kao i dominantnost hidrazo-keto oblika u odnosu na druge. Uticaj supstituenata na fenilnom jezgru na UV-Vis apsorpcione spektre takođe je veći nego uticaj rastvarača. NBO analize daju jasnu sliku o intramolekulskom prenosu naelektrisanja kod ispitivanih jedinjenja u zavisnosti od prisutnih supstituenata...Subject of this doctoral dissertation is the experimental and theoretical analysis of quinolone azo dyes and their precursors structure. Within the theses, the synthesis of azo dyes in which the role of the coupling components had the 4-hydroxy-2-quinolone while the diazo component was the corresponding p-substituted aniline, was carried out. First the synthesis of a series of N,N'-bisarylmalonamides (precursor) was performed. In-depth analysis (experimental and theoretical) of the prepared amides afforded the answers regarding the geometry and the reactivity of the tested precursors. The impact of the nature of the substituents on the phenyl nucleus, on the azo-hydrazone tautomerism in solution (with azo dyes), as well as the geometry and the reactivity of the precursor (N,N'-bisarilmalonamida) was studied. Also, the influence of solvents on the azo-hydrazone tautomerism of azo dyes as well as the solvent effect on the formation of intra- and intermolecular hydrogen bonds in N,N'-bisarylmalonamides was investigated. The analysis was performed using linear correlation free energy of solvation (LSER) using Kamlet-Taft and Catalan equations. Has been done the optimization of the tested compounds and examined the transmission of electronic effects of the application of quantum-chemical calculations (DFT). All compounds were synthesized according to the original or modified methods from the literature. The compounds were characterized by melting point, UV-Vis, FT-IR, 1H and 13C NMR spectra and elemental analysis. Determination of UV-Vis absorption maximum in a variety of solvents (spectroscopic grade) was carried out using a UV-Vis spectrophotometer. The effect of substituents on the transmission of electronic effects in N,N’-bisarylmalonamides was tested using simple and extended Hammett equations, as well as by Swain-Lupton equation. The results obtained by UV spectroscopic measurements (the N,N'-bisarilmalonamida) shows that the position of a UV absorption frequency much more affects the nature of substituents present on the phenyl ring than the properties of the solvent. Kamlet-Taft analysis showed that solvatochromism occurs mainly due dipolarity/polarizability solvent. Results obtained using the Hammett equation, indicate the existence of extended delocalization. The quantum mechanical calculations indicate that depending on the surrounding medium molecule N,N'-bisarilmalonamida can have various geometry. The results obtained by FT-IR and UV-Vis analysis of quinolone azo dyes indicate the existence of tautomerism and dominance of hydrazo-keto form. The influence of nature of the substituents on the phenyl nucleus in UV-Vis absorption spectra is also higher than the effect of the solvent. NBO analysis results give a clear picture of intramolecular charge transfer of the tested compounds according to the substituents present compounds..

Experimental and quantum-chemical studies of quinolone azo dyes and their precusors.

Predmet istraživanja ove doktorske disertacije bila je eksperimentalna i teorijska analiza strukture hinolonskih azo boja i njihovih prekursora. U okviru disertacije, izvršena je sinteza azo boja kod kojih je ulogu kuplujuće komponente imao 4-hidroksi- -2-hinolon, dok je diazo komponenta bila odgovarajući p-supstituisan anilin. Najpre je izvršena sinteza serije N,N’-bisarilmalonamida (prekursora hinolona) čija je detaljna analiza (eksperimentalna i teorijska) dala odgovore u vezi sa geometrijom i reaktivnošću ispitivanih prekursora. Proučavan je uticaj supstituenata fenilnog jezgra, na azo-hidrazon tautomeriju u rastvorima (kod azo boja), kao i na geometriju i reaktivnost prekursora (kod N,N’-bisarilmalonamida). Takođe, proučavan je uticaj i rastvarača na formiranje intra- i intermolekulske vodonične veze kod N,N’-bisarilmalonamida. Izvršena je analiza uticaja rastvarača na apsorpcione spektre ispitivanih jedinjenja primenom linearne korelacije energije solvatacije (LSER) uz korišćenje Kamlet-Taftove (Kamlet-Taft) i Katalanove (Catalán) jednačine. Urađena je i optimizacija geometrije ispitivanih jedinjenja i proučeno je prenošenje elektronskih efekata primenom kvantno-hemijskih proračuna (DFT). Sva jedinjenja sintetisana su prema originalnim ili modifikovanim metodama iz literature. Jedinjenja su okarakterisana temperaturama topljenja, UV-Vis, FT-IR, 1H i 13C NMR spektrima i elementarnom analizom. Na osnovu spektralnih podataka utvrđena je struktura tautomernih oblika boja. UV-Vis apsorpcioni maksimumi određeni su u različitim rastvaračima (spektroskopske čistoće). Uticaj supstituenata na prenošenje elektronskih efekata kod N,N’-bisarilmalonamida ispitan je primenom jednoparametarske i dvoparametarske Hametove (Hammett) jednačine, kao i primenom Svain-Luptonove (Swain-Lupton) jednačine. Rezultati dobijeni UV-spektroskopskim merenjima (kod N,N'-bisarilmalonamida) pokazuju, da na položaj UV-apsorpcionih frekvencija mnogo više utiče prisutni supstituent na fenilnom prstenu, nego svojstva rastvarača. Kamlet-Taft analiza je pokazala da solvatohromizam nastaje najvećim delom zbog dipolarnosti/polarizabilnosti rastvarača. Rezultati dobijeni Hametovom jednačinom ukazuju na postojanje proširene delokalizacije. Kvantno mehanički poračuni ukazuju da u zavisnosti od okolnog medijuma molekuli N,N'-bisarilmalonamida mogu imati različitu geometriju. Rezultati dobijeni FT-IR i UV-Vis analizom hinolonskih boja pokazuju postojanje tautomerije kao i dominantnost hidrazo-keto oblika u odnosu na druge. Uticaj supstituenata na fenilnom jezgru na UV-Vis apsorpcione spektre takođe je veći nego uticaj rastvarača. NBO analize daju jasnu sliku o intramolekulskom prenosu naelektrisanja kod ispitivanih jedinjenja u zavisnosti od prisutnih supstituenata...Subject of this doctoral dissertation is the experimental and theoretical analysis of quinolone azo dyes and their precursors structure. Within the theses, the synthesis of azo dyes in which the role of the coupling components had the 4-hydroxy-2-quinolone while the diazo component was the corresponding p-substituted aniline, was carried out. First the synthesis of a series of N,N'-bisarylmalonamides (precursor) was performed. In-depth analysis (experimental and theoretical) of the prepared amides afforded the answers regarding the geometry and the reactivity of the tested precursors. The impact of the nature of the substituents on the phenyl nucleus, on the azo-hydrazone tautomerism in solution (with azo dyes), as well as the geometry and the reactivity of the precursor (N,N'-bisarilmalonamida) was studied. Also, the influence of solvents on the azo-hydrazone tautomerism of azo dyes as well as the solvent effect on the formation of intra- and intermolecular hydrogen bonds in N,N'-bisarylmalonamides was investigated. The analysis was performed using linear correlation free energy of solvation (LSER) using Kamlet-Taft and Catalan equations. Has been done the optimization of the tested compounds and examined the transmission of electronic effects of the application of quantum-chemical calculations (DFT). All compounds were synthesized according to the original or modified methods from the literature. The compounds were characterized by melting point, UV-Vis, FT-IR, 1H and 13C NMR spectra and elemental analysis. Determination of UV-Vis absorption maximum in a variety of solvents (spectroscopic grade) was carried out using a UV-Vis spectrophotometer. The effect of substituents on the transmission of electronic effects in N,N’-bisarylmalonamides was tested using simple and extended Hammett equations, as well as by Swain-Lupton equation. The results obtained by UV spectroscopic measurements (the N,N'-bisarilmalonamida) shows that the position of a UV absorption frequency much more affects the nature of substituents present on the phenyl ring than the properties of the solvent. Kamlet-Taft analysis showed that solvatochromism occurs mainly due dipolarity/polarizability solvent. Results obtained using the Hammett equation, indicate the existence of extended delocalization. The quantum mechanical calculations indicate that depending on the surrounding medium molecule N,N'-bisarilmalonamida can have various geometry. The results obtained by FT-IR and UV-Vis analysis of quinolone azo dyes indicate the existence of tautomerism and dominance of hydrazo-keto form. The influence of nature of the substituents on the phenyl nucleus in UV-Vis absorption spectra is also higher than the effect of the solvent. NBO analysis results give a clear picture of intramolecular charge transfer of the tested compounds according to the substituents present compounds..