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Association between fibroblast growth factor 23 and bone loss in liver transplant candidates
No full textUvod: Jetrena osteodistrofija (engl. hepatic osteodistrophy, HO) je koštano-mineralni poremećaj u kandidata za ortotopnu transplantaciju jetre (OTJ) koju obilježava gubitak koštane mase i sklonost prijelomima. Čimbenik rasta fibroblasta 23 (engl. fibroblast growth factor 23, FGF23) regulira metabolizam fosfata i vitamina D, a povećane koncentracije se povezuju s gubitkom koštane mase i osteoporotskim prijelomima. Cilj ovog istraživanja je bio ispitati povezanost gubitka koštane mase i koncentracije intaktnog FGF23-a (engl. intact FGF23, iFGF23) u kandidata za OTJ.
Ispitanici i metode: U istraživanje su uključeni odrasli kandidati za OTJ. Gubitak koštane mase (osteopenija ili osteoporoza) je dijagnosticiran s pomoću denzitometrije kosti X-zrakama dvostruke prodornosti (DXA), a prijelomi kralježnice standardnim radiološkim snimkama. Izmjerene su koncentracije parametara koštano-mineralnog metabolizma, upale, inzulinske rezistencije, iFGF23 i aktivnost koštane alkalne fosfataze (BALP) u krvi. Ispitanici su podijeljeni u skupinu bez i s gubitkom koštane mase.
Rezultati: U istraživanje je uključeno 90 ispitanika (40 u skupini bez, a 50 u skupini s gubitkom koštane mase). Pojavnost gubitka koštane mase iznosila je 55,6%, a prijeloma kralježnice 48,9%. Nije bilo razlike statistički značajne razlike u parametrima koštano-mineralnog metabolizma, upale, inzulinske rezistencije te iFGF23-a između promatranih skupina. Aktivnost BALP-a bila je povećana u ispitanika s gubitkom koštane mase. Ženski spol i veća aktivnost BALP-a nezavisni su čimbenici rizika gubitka koštane mase, a starija životna dob prijeloma. Aktivnost BALP-a značajno je negativno korelirala s nalazom DXA.
Zaključci: Pojavnost gubitka koštane mase i osteoporotskih prijeloma kralježnice u kandidata za OTJ je veća nego u zdravoj populaciji. Koncentracija iFGF23-a nije povezana s gubitkom koštane mase.Introduction: Hepatic osteodystrophy (HO) is a bone-mineral disorder in orthotopic liver transplantation (OLT) candidates that leads to bone loss and tendency to fractures. Fibroblast growth factor 23 (FGF23) regulates phosphate and vitamin D metabolism, and is associated with bone loss and fragility fractures. The aim of this study was to examine the relationship between bone loss and the concentration of intact FGF23 (iFGF23) in OLT candidates.
Patients and methods: Adult OLT candidates were included in the study. Bone loss (osteopenia or osteoporosis) was diagnosed using dual-energy X-ray absorptiometry (DXA), and spinal fractures by standard radiological imaging. Parameters of bone-mineral metabolism, inflammation, insulin resistance, iFGF23 and bone alkaline phosphatase (BALP) activity were measured in blood. Patients were divided into groups with and without bone loss.
Results: Ninety (90) patients were included in the study (40 in the group without and 50 in the group with bone loss). The bone loss prevalence was 55.6% and vertebral fractures 48.9%. No significant differences in parameters of bone-mineral metabolism, inflammation, insuline resistance and iFGF23 were found between groups. Group with bone loss had higher BALP activity. Female gender and higher values of bone alkaline phosphatase were independent risk factors for bone loss, while older age was for fractures. BALP activity significantly negatively correlated with DXA results.
Conclusions: Prevalence of bone loss and osteoporotic fractures among OLT candidates is higher than in healthy population. No association exists between iFGF23 concentration and bone loss
Trends in newspaper criticism of Croatian feature fiction films from 2001 to 2019
No full textU središtu je ove disertacije znanstveno istraživanje suvremene novinske filmske kritike hrvatskih dugometražnih igranih filmova. Primjenom različitih metoda analiza medijskog teksta (prvenstveno kvantitativno-kvalitativnom analizom sadržaja) i dubinskim intervjuima s kritičarima dnevnih novina analizirani su različiti aspekti novinskih kritika i hrvatskih filmova. Cilj je bio ovim istraživanjem ukazati i na osobitosti suvremene hrvatske novinske filmske kritike. Istraženi su, nadalje, trendovi i promjene u načinu praćenja, analiziranja i kritičkog vrednovanja hrvatskog dugometražnog igranog filma u dnevnom tisku u kontekstu hrvatskog sociokulturnog okruženja u 21. stoljeću. Pokazalo se kako se u razdoblju od 2001. do 2019. godine u dnevnim novinama kritička recepcija hrvatskog filma promijenila iz neutralne u pretežno pozitivnu, te se utvrdilo povezivanje zaključaka kritika i širih društvenih pitanja, veća razina afirmativnosti kritike prema filmovima za koje se smatra da ukazuju na aktualne društvene probleme, te mala razina senzacionalizma uredničkih naslova kritika. Također su predstavljeni, sintetizirani, analizirani i komentirani rezultati pripremnog istraživanja, a kojim se utvrdilo, uz analizu kritičarske argumentacije i društvenog konteksta u navedenom razdoblju, koji su kritički najpozitivnije, a koji najnegativnije ocijenjeni hrvatski igrani filmovi, redatelji i žanrovi, na koje načine hrvatski igrani film pridonosi pluralizmu predstavljanja društvenih tema. Rezultati ovog istraživanja pružaju znanstvene uvide u osobitosti i trendove suvremene hrvatske novinske filmske kritike, a što predstavlja novost u nacionalnoj znanstvenoj literaturi i znanstveni doprinos istraživanju hrvatskog novinarstva. Utvrđivanjem osobitosti suvremenog hrvatskog dugometražnog igranog filma kao masovnog medija današnjice iz perspektive dnevne novinske filmske kritike, u kontekstu informacijskih i komunikacijskih znanosti (iz grana novinarstva i masovnih medija) i znanosti o umjetnosti (iz grane filmologije), ova je disertacija dala i relevantan multidisciplinarni doprinos proučavanju suvremenog hrvatskog filma.The focus of this doctoral dissertation is the scientific study of contemporary Croatian newspaper film criticism of Croatian feature films. Different aspects of newspaper criticism and Croatian cinema were analysed using different methods of media text analysis (primarily quantitative and qualitative content analysis) and in-depth interviews with daily newspaper critics. The main aim of the research was to show the specificities of contemporary Croatian newspaper film criticism. Furthermore, trends and changes in the way of covering, analysing, and critically evaluating Croatian feature films in the daily press in the context of the Croatian socio-cultural environment in the 21st century were explored. The research shows how in the period from 2001 to 2019, the critical reception of Croatian films in the daily newspapers changed from neutral to predominantly positive, the conclusions of critics were connected to broader social issues, there was a higher level of affirmative criticism towards films that were considered to indicate on current social problems, and there was a low level of sensationalism in editorial headlines. It also presents, synthesizes, analyses, and comments on the results of the preliminary research that determined, always along with the analysis of critical arguments and the social context in the
mentioned period, which are the most positive and most negatively evaluated Croatian feature films, directors and genres, and in which ways Croatian cinema contributes to the pluralism of the representation of social topics.
The results of this research provide scientific insights into the specificities and trends of contemporary Croatian newspaper film criticism, which is a novelty in the national scientific literature and a scientific contribution to the research of Croatian journalism. By establishing the specificities of the contemporary Croatian feature film as contemporary mass media from the perspective of daily newspaper film criticism, in the context of Information and Communication
sciences (Journalism and Mass Media) and Art Science (Filmology), this dissertation also made a relevant multidisciplinary contribution to the study of contemporary Croatian cinema. The dissertation is divided into nine chapters. In the introductory chapter, the subject of the dissertation, the research objectives and hypotheses, the structure of the dissertation, a review of the literature important for the theoretical treatment of the topic and the scientific contribution of
the work are presented. The second chapter describes the basic concepts important for understanding the content of the dissertation and their main features: journalistic genres, criticism and newspaper criticism, film criticism and newspaper film criticism. The third chapter deals with the origin and development of film criticism in the world and in Croatia, and then with the Croatian newspaper film criticism and Croatian feature film in the 21st century: critical reception of Croatian film directors, genres of Croatian feature film and analysis of social themes and subjects in Croatian film. The fourth chapter describes the research methodology: all hypotheses were tested by quantitative-qualitative content analysis and in-depth interviews, and the dissertation also uses inferential statistics in order to formally test hypothesis H3. At the end of the chapter, the results of the research are presented, i.e. the analysis and comparison of the results of the conducted
research, which prove each of the 4 hypotheses. The fifth chapter is the discussion, and the sixth is the conclusion of the entire dissertation, especially the research results. An overview of scientific literature, is listed in the seventh chapter, appendices (code sheet, in-depth interview protocol, and list of newspaper reviews from printed editions and online editions) in the eighth, and the author's biography and published works in the ninth. The dissertation determined how the critical reception of the Croatian feature films changed from neutral to predominantly positive during the period. Critical reception can be described by a neutral (average) average rating of 2.88 in the first year of research, 2.89 in the first three and four years, and 2.90 in the first five years of research, while at the end of the period covered by the research,
critical reception is predominantly positive, as assumed in the hypothesis, with a score of 3.66 in the last year of research, 3.51 in the last three years and 3.5 in the last 4 years. The difference in the earlier and later periods of the analysed period is also visible in the result pointing that, according to critics' evaluations, extremely bad films are produced less often in later periods, and that in later periods there are more films rated moderately and extremely positively. Critics point out that they link their negative critical reception of Croatian films (and that of their colleagues
from other daily newspapers) to the 1990s, and not to films from the beginning of the 21st century, for which they give a relatively low, but still average, rating. It was established that newspaper reviews of Croatian feature films are characterized by drawing conclusions in connection with wider social issues, thus confirming the theoretical assumptions of newspaper film criticism that Žigo and other theorists of criticism highlighted in their works. 29% of reviews were characterized by a strong level of conclusions regarding social issues, 51% fair, 20% moderate, and 0.68% low. The average recorded level of drawing conclusions in connection with broader social issues in all three analysed lists is 4.08. During the years covered by the research, there were no significant deviations: the lowest level of 3.81 was recorded in 2003 and 2018, and the highest 4.32 was recorded in 2009, so in all the researched years the average level was considerable. Critics point out that the reason for drawing conclusions in connection with broader social issues, apart from their critical interests, are the topics that Croatian films deal with, because Croatian cinematography less often films escapist genre productions, and more often dramas from Croatian everyday life. It was also established that Croatian newspaper film critics predominantly wrote more affirmatively about Croatian feature films that they considered to indicate current social problems, than about those that did not. Films rated with extremely and moderately positive reviews had a
fair level of pointing out social problems (4.34 and 4.06), as well as neutral (average) rated ones (3.54), while moderately and extremely negatively rated films had a moderate level of pointing out to social problems (3.04 and 2.78). The research showed that critics mostly emphasize that they value socially relevant films, but only if they are of high quality, which was also confirmed by the research of their reviews. There are several examples according to which it can be noted
that social criticism by itself cannot bring positive criticism to a film that does not have the appropriate qualities. Thus, socially critical films received generally more positive reviews than socially non-critical ones due to the greater overall quality that most of them were distinguished by, and not only because of film critics' affinity towards social criticism. The editorial titles of criticism of Croatian feature films in Croatian daily newspapers were to a small extent sensationalistic, and mostly objectively reflected the views of the authors. The titles studied were, depending on the critics and editors, interesting, informative, funny, intelligent, ambiguous, likeable, intriguing or provocative, and the level of sensationalism ranged from the level of not at all (36%), very little (51%) to moderate (13 %), with an average low level of 1.78, without quite or extremely sensational headlines. Titles that are moderately sensational are often characterized by exaggeration, they often refer to popular culture (songs, sayings, books and films), but mostly objectively reflect the critic's attitude. Editors generally readily accepted the most intriguing theses, quips or comparisons offered by critics in their texts. Critics point out that newspaper headlines can be sensationalistic and reflect the author's position, just as they can falsify the author's position without being sensationalist at all, and the analysis of their criticisms shows that there were all the cases mentioned, so the sensationalism of the headlines should not be equated with the non-objective presentation of the critic's position. The most positively evaluated directors by critics among those with three or more films from 2001. till 2019. were Rajko Grlić, Ognjen Sviličić, Zrinko Ogresta, Vinko Brešan, Antonio Nuić, Arsen Anton Ostojić, Dalibor Matanić and Kristijan Milić, with a note that according to critics' ratings, filsm made by Grlić, Brešan and Ogresta had the most consistent quality. The most negatively evaluated directors among those with two or more films in this period are Vicko Ruić, Zdravko Mustać, Filip Šovagović, Jakov Sedlar, Fadil Hadžić and Krsto Papić. No female director made 3 feature films in this period, and only Snježana Tribuson made 2. Nevertheless, women directed some of the highest-rated films in this period. At the top of the list is Hana Jušić, Dana Budisavljević and Ivona Juka are among the highly respected, followed by Snježana Tribuson. The most positively rated Croatian films by newspaper film critics are Hana Jušić's Quit Staring at my Plate and Dalibor Matanić's High Noon, while the third on the list is A stranger by Bobo Jelčić. The most negatively rated Croatian films by newspaper film critics are The Recollection Thief and Seraphim, the Lighthouse Keeper's Son by Vicko Ruić, followed by Remembrance of Georgia by Jakov Sedlar and The Enchanting Porkers by Ivan Livaković. Croatian films in the 21st century that received the most positive reviews most often belong to the genre of social-psychological drama contemporary drama, the second genre is action, while the third is war drama. Among the genres whose representatives received the most negative reviews in the 21st century, road films, erotic films and biographical historical dramas are leading the way. Thematically speaking, global themes were definitely never the focus of Croatian directors, who mostly dealt with domestic problems and motives. Croatian cinematography dealt with the subject of violence and torture in many ways, intensively and, according to critics, competently, from historical (from the Second World War to the Croatian Homeland War) to contemporary subjects (terror against sexual minorities in Croatian society, fan hooligan violence), and the treatment of these subjects created some of the most appreciated film productions of that period. Regarding national minorities, the Serbian minority in Croatia was the most common film inspiration. Croatian films undoubtedly point to the activities of economic and political power holders, but cautiously and somewhat abstractly. Even the bravest directors did not pass their critical judgment on some specific political names from Croatian politics through their films, and with the exception of Vinko Brešan, almost no one dealt more seriously with the characters of Croatian prime ministers and presidents, but even in his films we can see general characters of politicians who cannot be related for some concrete Croatian political figures. There are very few films that have caused wider social controversies. Analysing the diversity of the angle of view of individual directors, i.e. their approach in the presentation of key social themes in Croatian feature films, we come to the conclusion that the most socially critical director was Vinko Brešan (with the themes of war crimes of Croatian soldiers, sexual abuse of children by priests and political manipulation), and then Branko Schmidt (with topics about young thugs and drug addicts, crimes within the healthcare system and
pedophilia in the Church). This dissertation provides a relevant scientific contribution to the study of contemporary
newspaper film criticism, as well as contemporary Croatian journalism in general. The results obtained in this doctoral dissertation provide scientific insight into the specificities of contemporary Croatian newspaper film criticism, but they also contribute to the positioning of newspaper film criticism in the context of journalistic discourse, pointing to the specifics of
newspaper film criticism as a journalistic genre which, in this sense, should be understood beyond the narrow links with literature and filmology, in the context of daily newspapers in which reviews are published and by connecting the conclusions with socially relevant topics. It should be emphasized that the proposed research model, taking into account the specifics of theatrical and literary works, could be applied to newspaper literary and theatrical criticism
Degradation study of lipoglycodepsipeptide antibiotic ramoplanin by liquid chromatography and mass spectrometry
No full textU borbi protiv bakterijske rezistencije, ciklički lipoglikodepsipeptid ramoplanin pojavio se kao novi obećavajući antibiotski lijek. U ovom radu je razvijena, validirana i upotrjebljena metoda tekućinske kromatografije za praćenje stabilnosti ramoplanina, u čvrstom stanju i u otopini. Studija forsirane razgradnje provedena je podvrgavanjem uzorka različitim stresnim uvjetima (kisela i bazična hidroliza, oksidacija, vlaga, temperatura i svjetlo) te su opaženi razgradni produkti razjašnjeni spektrometrijom masa. Istraživanje je otkrilo kako je hidroliza laktonskog prstena najvažniji degradacijski put molekule. Međutim, opaženi su i drugi značajni putevi degradacije. Nadalje, ramoplanin je formuliran u vodenim otopinama koristeći nekoliko različitih pomoćnih tvari te je provedena stabilitetna studija pri 25 °C/60 % RV i 40 °C/75 % RV. Među ispitanim pomoćnim tvarima, polisorbat 20, Kolliphor® RH 40 i kolin klorid pokazali su važan stabilizacijski učinak na degradaciju ramoplanina.In the fight against antimicrobial resistance, a cyclic lipoglycodepsipeptide ramoplanin emerged as a new promising antibacterial regimen. In the present work, an LC method was developed, validated and used during stability testing of ramoplanin, in solid state and in solution. Forced degradation study was performed by subjecting the sample to different stress conditions (acid and base hydrolysis, oxidation, humidity, heat and light) and the observed degradation products were elucidated using mass spectrometry. The study revealed that the most significant degradation path of the molecule is hydrolysis of its lactone ring. However, other significant degradation routs were also observed. Furthermore, ramoplanin was formulated in aqueous solutions using several different excipients and a stability study was conducted at 25 °C/60 % RH and 40 °C/75 % RH. Among the tested excipients, polysorbate 20, Kolliphor® RH 40 and choline chloride were found to have an important stabilizing effect on the degradation of ramoplanin
Quantum chemical calculations and machnie learning in predicting bioactivity of new compounds
No full textMale molekule mogu interagirati s biološkim makromolekulama i tako utjecati na homeostazu organizma. U okviru ovoga doktorskog rada računalno su istraženi odabrani kemijski spojevi kao potencijalni antimikrobni agensi i/ili inhibitori kolinesteraza. Najvažnije interakcije malih molekula s makromolekulama određene su metodama molekularnog dokiranja: 1. novorazvijena metoda tenzorske dekompozicije trajektorija ab initio molekularne dinamike te 2. kvantno-kemijsko Monte Carlo dokiranje unutar aktivnog mjesta enzima. Molekularno dokiranje ab initio molekularnom dinamikom uključuje protokol strojnog učenja za određivanje duljine trajanja simulacija kada su uzorkovani potpuni konfiguracijski prostori. Kvantno-kemijsko Monte Carlo dokiranje podrazumijeva uzorkovanje struktura putem generiranja slučajnih konfiguracija sustava (aktivno mjesto enzima i mala molekula) te kvantno-kemijske proračune energije. Ekstenzivnom primjenom strojnog učenja uspostavljeni su najbolji mogući multivarijatni linearni regresijski modeli koji povezuju biološku aktivnost promatranih spojeva s njihovim teorijski uzorkovanim plohama potencijalne energije. Dobiveni rezultati predstavljat će osnovu za daljnja istraživanja najvažnijih interakcija malih molekula s kolinesterazama i za predviđanje bioaktivnosti te "pametan" dizajn novih bioaktivnih molekula.Small molecules can interact with biological macromolecules and thus affect the organism's homeostasis. Within this doctoral dissertation, selected chemical compounds were theoretically investigated as potential antimicrobial agents and/or cholinesterase inhibitors. The most important interactions of small molecules with macromolecules were determined by molecular docking methods: 1. newly developed method of tensor decomposition of ab initio molecular dynamics trajectories and 2. quantum-chemical Monte Carlo docking within the active site of the enzyme. Molecular docking by ab initio molecular dynamics includes a machine learning protocol for determining the length of simulations where complete configuration spaces are sampled. Quantum-chemical Monte Carlo docking implies sampling of structures through the generation of random system configurations (enzyme active site and small molecule) and quantum-chemical energy calculations. Through the extensive application of machine learning, the best possible multivariate linear regression models that connect the biological activity of the observed compounds with their theoretically sampled potential energy surfaces were established. The obtained results will represent the basis for further research of the most important interactions of small molecules with cholinesterases as well as the prediction of bioactivity and the "smart" design of new bioactive molecule
Connections between Croatian and Italian painting between 1872 and 1919
No full textOva disertacija istražuje i izdvaja komponentu talijanskih elemenata u slikarstvu hrvatskih autora u zadanom razdoblju od ostalih srednjoeuropskih utjecaja. Njihovo međusobno razlikovanje, kako će se tijekom razrade pokazati, nije uvijek jasno razgraničeno te zahtijeva priznavanje difuzne naravi nijansi u prijelazima. Ova je činjenica rezultat višestrukih čimbenika: od važnosti kulturne razmjene između Italije i prekoalpskih zemalja, koja se odvijala kroz nekoliko različitih kanala, do povijesne uvjetovanosti povezanosti dijelova sjeverne Italije s Austrijom te, konkretno, s austrijskom upravom. Uže područje rada sačinjavaju dijelovi opusa hrvatskih slikara, koji su nastali u, izravnom ili posrednom, kontaktu s talijanskim kulturnim krugom u razdoblju od 1872. do 1919. godine. Kao početna granica ove disertacije uzete su 1870-te godine jer označavaju odlazak prve trojice predstavnika hrvatskog slikarstva: Ferdinanda Quiquereza, Izidora Kršnjavoga i Nikole Mašića, s Akademije u Münchenu na putovanje u Italiju prema ruti: Venecija, Rim, Napulj (Capri). Završna 1919. godina označava kraj prvog razdoblja izložbi Proljetnog salona (1916.–1919.), kao prijelazni period koji je omogućio snažniji modernistički zamah ostvaren nakon rata te je označen ispreplitanjima jugendstilskih “zaostataka“ i naznaka avangardnijih pristupa u umjetnosti. Cilj istraživanja je obrada i interpretacija segmenta hrvatskog slikarstva 1872.–1919. na osnovi njegovih poveznica s talijanskim kulturnim krugom, koji do sada nije bio sustavno obrađen niti interpretiran, pri čemu su uporabljene uvriježene metode povijesti umjetnosti: formalna, komparativna i ikonografska analiza pojedinih djela, problemi stila i tipologije, terenski rad, proučavanje arhivske građe i objavljene literature. Smatramo da će se sagledavanjem situacije iz ovoga kuta doći do novih spoznaja o pojedinačnim opusima autora, ali i o cjelini ovog važnog segmenta hrvatskog slikarstva.Italy of the 19th and early 20th century is characterised by the specific artistic legacy, as well as a specific relationship towards modernism, that is a constant subject of research in international publications end exhibitions. Its cultural role as the unavoidable destination in the context of the phenomenon of the Grand Tour is markedly important, especially during the course of the 19th century. Travels of the Italians to the European countries north of Alps, as well as the numerous visits and stays of the foreigners in Italy (which would occasionaly turn into permanent residence) contributed to the formation of a vibrant Italian artistic scene in a complex exchange of experiences. While acknowledging Italian specific characteristics and contributions to the European artistic scene, it is nevertheless important to recognise its interweaving with the Mediterranean and (Middle)European traditions, especially those of the French, Austrian and German provenance. The aforementioned was facilitated by historical circumstances, such as the sporadic Austrian government over certain parts of northern Italy. The painter Giovanni Segantini played an especially prominent role in connecting Italy with the rest of Europe due to his extreme popularity and international presence. The establishment of international exhibitions, such as la Biennale di Venezia in 1895, brings new impetus to this interchange. Traditionally strong connections between Italy and Croatia, especially its maritime area, lose its intensity after the fall of the Republic of Venice in the year 1797. However they do not disappear altogether. Although Croatian artists were trained predominantly at the Academies in Vienna and Munich at the time, Italy was their third important destination chosen over two reasons: firstly for the reasons of direct training at the Italian Academies, and secondly as the destination of the European trend of travel to Italy, as the land of classical heritage, natural beauty and specific quality of southern light. Additional historical connection between the two countries was constituted by the fact of the joint Austrian government over Croatia and north Italian regions of Trentino and parts of Friuli-Venezia Giulia by the end of World War I, as well as Veneto during the periods from 1797 to 1805 and from 1815 to 1866. It is important to take notice of the fact that one of the most prolific and vibrant artistic centres of the period, Paris was the rarest choice of Croatian 19th century painters. Connections between Croatian and Italian painting between 1872 and 1919 were realised within three different artistic tendecies of the European art at the turn of the 20th century: firstly the practice of the plein-air landscape study in Italy as preparation for studio compositions; secondly the different manifestations of symbolism; and lastly the inclinations towards avanguard components in the painting of the early 20th century. The book Corot in Italy: Open-Air Painting and the Classical-Landscape Tradition written by Peter Galassi in 1991, as well as the exhibition In the Light of Italy: Corot and Early Open-Air Painting held in 1996–1997 in Washington related to it, proved to be the key in understanding the context of the plein-air study painting in Italy as preparatory work for grand studio compositions. It explaines how the tradition of the landscape and cityscape study in Italy founded in 1780s was codified by the Pierre-Henri de Valenciennes' influential 1800 treatise Elémens de perspective practique, à l'usage des artistes, suivis de Réflexions et conseils à un élève sur la peinture, et particulièrement sur le genre du paysage. Camille Corot’s Italian studies from the period between 1825 and 1828 represented the culmination in this strain of painting. Their purpose was didactic and their main characteristics were: painting in the open in direct study of nature, the effect of sketch due to the rapid brushstroke and spontaneous approach to painting, the use of oil technique usually on paper mounted onto cardboard, the codified topography of motifs following the ‘prescribed’ Italian itinerary, painting during summer months as well as the conscious choosing of the noon or more rarely early evening lighting, the choice to depict fragments of simple, anonymous, rural architecture or details of vegetation, for instance motifs of a tree or treetrunk. Although the tradition of plein-air study could be found elsewhere in Europe at the beginning of the 19th century, Italy was the key area at the turn of the 19th century where it flourished more intensly in the international context of artists and travellers from all around Europe. This was especially true of its regions around Rome and Naples. The significance of the ambiance of (southern) Italy for the history of the European landscape painting was noticed by the Croatian art critic Josip Pasarić in 1902. Seen in this light the relationship between the studio composition of the academic realism and spontaneous plein-air study painting becomes complementary. Galassi explains that the Scuola di Posillipo was formed in the Naples area during the second quarter of the 19th century as a provincial echo of the international school of painters in Italy practicing plein-air study. Moreover, it was founded by a Dutch, Anton Sminck van Pitloo. It formed the basis on which the later Neapolitan schools of painting in the second half of ottocento were built, enriching their expression further through contacts with the Florentine Macchiaioli and contemporary French painting. The next important Italian destination for Croatian painters was Venice. After a period of crisis it succeded in forming a unique expression through the synthesis of its distinctive tradition permeated by the artistic influxes from the rest of Italy and wider international contacts (especially after the establishment of the Venice Biennale exhibitions in 1895). Following the described complexity of the overall context the connections between Croatian and Italian painting should be evaluated in the elaborated terms of interdependences on wider European scene. Croatian painters Izidor Kršnjavi, Ferdinand Quiquerez, Nikola Mašić and Bela Čikoš Sesija set off to Rome and Naples from the Academy in Munich, where the tradition of the Italian journey was especially long cherished and formed an inseparable part of the education process. Their production of Italian plein-air landscape and cityscape studies should first and foremost be interpreted in the context of the tradition of the international school of painters in southern Italy established in classicism, onto which Italian ottocento schools of painting build upon. In Quiquerez and Kršnjavi the influence of Corot's legacy transformed through the painting of the Venetians Ippolito Caffi (more pronounced in Quiquerez) and Guglielmo Ciardi with his interpretation of the Macchiaioli and Scuola di Resina style of painting (more felt in Kršnjavi) can be discerned. Influences by Giacomo Favretto often mentioned in critique turn out to be nonexistent. In the painting of Nikola Mašić, on the other hand, within the same tradition connections to the Neapolitan painting of the second half of ottocento are more clearly articulated, namely those with: Filippo Palizzi, Mariano Fortuny, Francesco Paolo Michetti and Scuola di Resina. Key to the understanding of Mašić's painting however prove to be the painting of Filippo Palizzi. Just like Mašić, Filippo Palizzi enjoyed depicting animal world and was primarily a painter of genre scenes with occasional landscape studies done in macchia technique. Large part of Mašić's oeuvre after 1880 was formed by large scale Handtuchformats portraying genre scenes in accordance with Arcadian transformation of the legacy of Filippo Palizzi in the work of Francesco Paolo Michetti, alongside colouristic virtuosity and glitter of the embellished realism of the Catalan Mariano Fortuny y Carbò, who was also a protagonist on the Neapolitan scene of the second half of the 19th century. The introduction of the element of the modified legacy of Filippo Palizzi in combination with the fortunylike chromatics through interpretations of Francesco Paolo Michetti, as explained in the thesis, sets out a new context for the fortunismo of Nikola Mašić. Also, some examples of Mašić's painting, such as Slikar u bari (Painter in the marshes), 1878–80., Zatvorena vrata (Closed door) study, 1880., or a small detail depicting a flock of geese just above the water surface on the painting Guščarica na Savi (Goose Girl by the River Sava), 1880–81., display a speecific pennellata technique that creates vibrant surfaces in the manner of Antonio Mancini, whose painting is for the first time mentioned in connection to Nikola Mašić's production. Within this same prolonged classicist tradition of the landscape and cityscape study, less than two decades after Quiquerez, Kršnjavi and Mašić had sojourned there, Bela Čikoš Sesija also episodically embraced the premises of the southern Italian landscape and cityscape painting in the Neapolitan area. His plein-air landscape and cityscape studies with motifs focused on details, characterised by formal reduction and constructed relation of light and shadow build upon the traditions of the international school in Italy, Neapolitan and Macchiaioli painting. Inclination towards rural simplicity in the choice of motifs seen in the paintings of Bela Čikoš was also the legacy of the international school of painters in Italy, continued in the Italian realist ottocento painting all the way to the Postmacchiaioli era of the last quarter of the 19th century, the period of Čikoš's southern Italian soujorn. Nocturnal cityscapes which Čikoš sketches in Italy prove to be transitory towards symbolist painting. Although the tradition of the execution of studies in the lighting of the early evening is well documented in the history of the painting of the international school in Italy, as well as there are well known instances of nocturnal scenes in the context of the Italian ottocento painting of realist provenance, such as the cityscape of Naples by Adriano Cecioni, the painter that connected Florentine Macchiaioli and southern Italian Scuola di Resina, these studies by Bela Čikoš should be understood as an indication towards his later symbolist expression. The latter is affirmed by the choice of the subject of Pietà in a southern Italian study from the year 1893. Everything considered, we come to the conclusion that the Italian episode of Bela Čikoš should not be taken as a divergence in his oeuvre, but rather as a typical formation path of a 19th century painter, witnessed by the example of Arnold Böcklin, himself being a pivotal protagonist of the European symbolism, who spent much of his life in Italy where, among other things, he painted realist landscapes. As opposed to the landscapes painted in Italy, the post Italian landscapes by Bela Čikoš should be considered in the context of the German variant of 'impressionism'. The other important centre of the Italian realist tradition was Florence and the Macchiaioli. Vinko Draganja and Mato Celestin Medović were trained there. Apart from being a student of the Florentine Academy, key to intrepretation of Draganja's painting turned out to be a so far overlooked detail from his Autobiography of his friendship with the Italian painter Domenico Pesenti. Pesenti's oeuvre is directly comparable to that of Vinko Draganja during his Italian years. As shown in the thesis for the first time, the affinity in the choice of themes and motifs, as well as the composition and painterly approach, characterised by the transformation of the Macchiaioli legacy, within its marginal and belated echos and emphasising more pronouncely the narrative component of the painting, can be discerned. Also, while interpreting this kind of painting, the names of the Induno brothers, Domenico and Gerolamo from Milan (Pesenti was trained in Lombardy) with their continuance of the tradition of a specific genre painting should not be overlooked. Mato Celestin Medović spent a prolonged period of unsystematic training in Italy from 1880 till 1886. Within this scope of time, he also sojourned in Florence meeting Vinko Draganja there and studying at the private school of Antonio Ciseri. Traditionally Medović's Italian years and his artistic training there were not considered very important, but rather the major significance was given to his later Munich training. During the research for this thesis however, I came to conclusion that Medović's Italian experience was far more important than earlier presumed. Through the analysis of representative pieces of Medović's portraits and religious compositions clear connections to his Florentine teacher Antonio Ciseri can be seen. In addition to that, Medović's familiarity with the painting of of the 'Florentine Alma-Tadema', Giovanni Muzzioli turns out to be of outmost importance for his artistic expression, which has been noticed for the first time here. Muzzioli was a famous Florentine painter whose popularity reached its peak during Medović's sojourn in the city and whose painting was characterised by a hybrid amalgam of history painting and European tradition of plein-air and genre, especially that of the Macchiaioli provenance. In the first ever display of comparative analysis between Medović's and Muzzioli oeuvres, compatibility in the choice of themes and motifs, painterly approach and style is shown. Both painters treat representative history painting in a skillful academic manner, while the plein-air, landscape, cityscape and genre studies showcase free and sketchy pennellata with the simplified and reduced to essentials painterly approach. Especially interesting in their oeuvres is a special hybrid category of the so called 'historic genre' (generismo antichizzante / la pittura ‘di genere’ in versione greca e romana / la pittura storica di genere), in which figures in antique costume are arranged and added into directly studied plein-air landscape. The biggest surprise was the discovery of the formidable influence of the Italian painting on Bakanal from 1893 by Medović, the painting that has been firmly and unanimously considered as the crown jewel of Medović’s Munich training and was previously almost exclusively connected to the style of painting of Karl Theodor Piloty. There were however some early examples in the Croatian art writings considering the compatibility between Medović’s emblematic painting and Muzzioli’s Al Tempio di Bacco from the year 1881. Ljubo Babić accused Medović of plagiarism, while Vera Kružić-Uchytil and Igor Zidić stood up for the Croatian painter. The first ever detailed analysis presented in the thesis confirms significant parallels in composition and style with the selected examples of Giovanni Muzzioli’s painting, as well as sets out a completely novel observation about the affinities with the Antonio Ciseri’s painting Il Martirio dei Maccabei, 1858.–1863. The analysis further brings us to the conclusion that in Medović’s Bakanal we are not dealing with the act of plagiarism, to use the words of Ljubo Babić, but rather with a legitimate reinterpretation of the existing models transformed through Medović’s specific semantics that imbues the painting with the possible meaning of social criticism. All taken into consideration, key to the interpretation and understanding of the work of Vinko Draganja and Mato Celestin Medović turn out to be the Postmacchiaioli context of Florence of the 1880s and oeuvres of the Italian authors Domenico Pesenti and Giovanni Muzzioli, whose art transforms the Macchiaioli legacy in a hybrid painting that combines modern principles of the Tuscan heritage with the narrative and historic elements in an academic manner. In addition, Medović’s Italian teacher Antonio Ciseri turns out to be far more important for his painting than it was earlier supposed. Historically the Croatian coast was strongly connected to Venice, which underwent an identity crisis of sorts after the downfall of the Republic of Venice in 1797. Following the unification of Italy in 1866, ties between Venice and the other Italian cities became ever stronger and through these contacts Venetian artists worked with new experiences, modifying them through the filter of the Venetian specific tradition creating a particular and characteristic synthesis. Almost simultaneously, Josip Lalić and Emanuel Vidović set off to Venice for artistic training. They spent the second half of the 1880s and the first half of the 1890s there, and Vidović would revisit the city on a lagoon continuously throughout his life. Both painters were formed there through the initial cityscape and landscape painting of the combined Venetian and Macchiaioli inspiration. Soon they left for a short sojourn in Milan, from where Lalić departed for Paris and Vidović returned to Venice of his destiny. Early phase of Emanuel Vidović's painting depicting cityscapes of Venice and Chioggia is characterised by the Macchiaioli inspiration transformed by Venetian tradition. Rather poorly documented biography and curriculum vitae, which has been reconstructed with the help of archival materials and literature for purposes of this research, limit our understanding of the oeuvre of Josip Lalić. Our interpretation of the latter is based on the examples of paintings from Croatian and Italian collections. In the Roman museums Galleria Nazionale d'Arte Moderna e Contemporanea di Roma and Galleria Comunale d'Arte Moderna e Contemporanea di Roma fourteen paintigs by Josip Lalić (with the additional three that were destroyed presumably due to a Second World War bombing) were discovered during the course of this research and were subsequently presented to the Croatian community of art historians. The analysis has shown that the early painting by Josip Lalić, it would seem, could be compared to Emanuel Vidović’s early works. In both cases we are dealing with small formats of realist landscapes and citiscapes and, with Lalić especially, genre scenes from the everyday life in the city. They were painted in the combined Venetian and Macchiaioli tradition of free pennellata and sketchy approach often depicting Venetian canals (especially in Vidović). Basic Venetian connections with their painting are found in the work of Ippolito Caffi and contemporaries Bartolomeo Bezzi, Pietro Fragiacomo and especially Guglielmo Ciardi, and in the case of Josip Lalić also Alessandro Milesi. Often propounded as Vidović’s Venetian model, the painter Giacomo Favretto does not turn out to be the key connection of reference in interpreting Vidović’s early painting. The painting of Ante Katunarić, who frequented the Academy in Rome during the period from 1892 till 1896, was formed through contacts with Emanuel Vidović during their joint year long stay in Chioggia in 1897. Virgil Meneghello-Dinčić is also mentioned in the context of these artistic sojourns in Venice and Chioggia together with Vidović and Katunarić. His painting of this period is however completely lost and for this reason was not presented in this chapter. As far as Ante Katunarić is concerned, his painting of the period is formed in relation to Emanuel Vidović, but the dispersion of the artist’s interests resulted in a significantly lower artistic quality of his work. Just as with Emanuel Vidović and Josip Lalić, here too we are dealing with the basic Venetian inspiration, Guglielmo Ciardi above all, combined with that of the Tuscan legacy of Macchiaioli. In Katunarić’s work however more pronounced influences of French painting can be felt, which should be understood in the context of Postmacchiaioli atmosphere that synthesised the Macchiaioli and French Impressionists legacy. Also, one shou
Association of serum concentrations of interleukins IL-18, IL-19, IL-21 and IL-22 with the etiopathogenesis and assessment of clinical activity of nonsegmental form of vitiligo
No full textVitiligo je stečeni, kronični idiopatski poremećaj pigmentacije koji se očituje pojavom depigmentiranih makula na koži, a nastaje zbog selektivnog gubitka melanocita. Autoimunosna teorija se smatra vodećom etiopatogetskom teorijom nastanka vitiliga. Citokini su ključni medijatori stanične komunikacije i imaju značajnu ulogu u razvoju, diferencijaciji i regulaciji upalnog odgovora koji dovodi do pojave autoimunosti. Stoga je cilj ovog istraživanja bilo ispitati povezanost nesegmentalnog oblika vitiliga i serumske koncentracije interleukina (IL) IL-18, IL-19, IL-21 i IL- 22 te dobivene vrijednosti usporediti s težinom kliničke slike, aktivnošću te trajanjem bolesti. U istraživanje je bilo uključeno 78 ispitanika, od kojih 52 bolesnika sa nesegmentalnim vitiligom i 26 ispitanika u kontrolnoj skupini. U skupini bolesnika s nesegmentalnim oblikom vitiliga su izmjerene značajno više serumske koncentracije IL-19 i IL-21 te niže serumske koncentracije IL-18 i IL-22 u odnosu na kontrolnu skupinu ispitanika. Nije pronađena značajnija korelacija između težine kliničke slike, aktivnosti i trajanja bolesti. Ovim istraživanjem je prvi puta do sada učinjena analiza serumskih koncentracija kombinacije citokina IL-18, IL-19, IL-21 i IL-22 te su po prvi puta određene serumske koncentracije IL-18 i IL-19. Rezultati ovog istraživanja mogu doprinijeti boljem razumijevanju kompleksne etiopatogeneze vitiliga, ali mogu i poslužiti kao prilog spoznaji za mogući razvoj ciljane terapije, uključivši i proizvodnju monoklonskih protutijela. S obzirom da je u ovo istraživanje bio uključen relativno mali broj ispitanika, potrebne su dodatne studije na većem broju ispitanika u različitim fazama bolesti koje bi razjasnile značenje IL-18, IL-19, IL-21 i IL-22 u etiopatogenezi i kliničkim značajkama ove bolesti, kao i u mogućem razvoju ciljane terapije.Vitiligo is an acquired, chronic idiopathic pigmentation disorder that presenting with depigmented macules, caused by the selective loss of melanocytes. The autoimmune theory is considered to be the leading aetiopathogetic theory of vitiligo. Cytokines are key mediators of cellular communication and play a significant role in the development, differentiation, and regulation of the autoimmune inflammatory response. The aim of this study was to determine the association between the non-segmental form of vitiligo and the interleukins (IL) IL-18, IL-19, IL-21 and IL- 22 by measuring the serum concentration of these interleukins and to compare them with clinical severity, activity and disease duration. Seventy-eight patients were included into this study, out of whom 52 patients with nonsegmental vitiligo and 26 patients in the control group. Significantly higher serum concentrations of IL-19 and IL-21 and lower serum concentrations of IL-18 and IL- 22 were assessed in the group of patients with non-segmental vitiligo compared to the control group. No significant correlation was found between the severity, activity, and duration of the disease. This study was the first so far to analyze serum concentrations of the combination of cytokines IL-18, IL-19, IL-21 and IL-22 and to determine serum concentrations of IL-18 and IL- 19. The results of this research might contribute to the better understanding of the complex aetiopathogenesis of vitiligo, but might also contribute to the development of targeted biological therapy, i.e. the production of monoclonal antibodies. Given that a relatively small number of subjects were included in this study, additional studies are needed on a larger number of patients at different stages of the disease to clarify the role of IL-18, IL-19, IL-21 and IL-22 in the aetiopathogenesis of vitligo, its clinical characteristics and in the potential development of targeted therapy
The role and development of sound editing in Croatian cinema from the 1940s to the 1970s
No full textCilj ovog rada je historiografskim pristupom popratiti te analizirati razvoj i ulogu montaže zvuka u hrvatskoj kinematografiji od 1940-ih do 1970-ih u kontekstu dugometražnog igranog filma, kako bi se pružio detaljan uvid u dostignuća i umjetničku praksu ove važne, a uglavnom zanemarene, filmske djelatnosti. Za bolje razumijevanje profesije montaže zvuka, i konteksta njenog nastanka, rad počinje povijesnim pregledom metoda i praksi ozvučavanja nijemog filma u američkoj kinematografiji, a potom daje komparativan pregled praksi hrvatske kinematografije. Već u razdoblju nijemog filma izdvaja se uporaba govora, šumova i glazbe, elemenata koji će stvarati zvučnu sliku budućeg zvučnog filma. Prvi zvučni filmovi projicirani su korištenjem različitih sustava, no prevladat će sustavi u kojima se slikovni i zvučni zapis filma nalaze na jednoj vrpci što će predstavljati temelj za razvoj profesije montaže zvuka. Zbog iznimno skromnih tehničkih i financijskih uvjeta hrvatske kinematografije, profesija montaže zvuka, u kontekstu dugometražnog filma, izdvojit će se u zasebno zanimanje tek krajem 1940-ih. Analizom zvučne slike svih dugometražnih igranih filmova nastalih između 1944. i 1970. (82 filmska djela) prati se razvoj montažnih postupaka na razini zvučne slike, sve do dosezanja visokog standarda profesije, što je omogućilo institucionaliziranje obrazovanja za montažu zvuka (ali i slike) osnivanjem Odsjeka montaže 1969. na ondašnjoj Kazališnoj akademiji na kojem će praktičnu nastavu voditi iskusni filmski montažeri s velikim znanjem i bogatim iskustvom koji će obrazovati iduću generaciju filmaša.The aim of this work is to historically track and analyse the development and role of sound editing in Croatian cinema from the 1940s to the 1970s in the context of feature-length fiction films, in order to provide a detailed insight into the achievements and artistic practices of this important but often neglected film profession. To better understand the profession of sound editing and the context of its emergence, this work begins with a historical overview of the methods and practices of sound accompaniment in American cinema during the silent film era, followed by a comparative analysis of practices in Croatian cinema. Even during the silent film era, the use of speech, sound effects, and music, elements that would create soundscapes of future sound films, was notable. The first sound films were projected using various reproduction systems, but the system where both the visual and audio segment of the film were on a single filmstrip would ultimately prevail, laying the foundation for the development of the sound editing profession. Due to extremely limited technical and financial resources, Croatian cinema in the 1930s regularly produced only commissioned and promotional films in which the sound was shaped during synchronization. The beginnings of the sound editor profession in Croatia are closely tied to employment opportunities, greatly aided by the establishment of the first film companies and eventually the Jadran film studio, which resulted in the production of the first feature-length fiction film in 1944, marking the start of continuous film production. The first use of the title sound editor in the context of feature-length fiction films is documented in the credits of the film Zastava in 1949. Despite the establishment of technological conditions and the development of post-production systems and tools in Croatian cinema, a major challenge was the education of film professionals for working with sound film. Sound editors predominantly educated themselves for their profession through apprenticeship under more experienced colleagues and learned through practice, later supplemented by various workshops and courses. The practice of apprenticeship for work on early sound films was a dominant form of education in other countries as well. Education for film editors (both sound and picture) became institutionalized in 1969 with the founding of the Editing Department at the today’s Academy of Dramatic Art, University of Zagreb. The continuous production of feature-length fiction films, noticeable from the 1950s onwards, allowed for the tracking of the development of the sound editing profession. Over the coming years and through film soundscapes analysis, it becomes evident that editing techniques became more diverse with various distinct solutions adopted, specific editing methods became integrated into the soundscapes of future films, the dramaturgy of soundscapes became more complex, and the overall believability of the soundscapes was achieved not only occasionally but consistently throughout the entire film. A significant turning point in achieving synchronization, which is essential for creating convincing soundscapes, is represented by the film Tko pjeva zlo ne misli (1970), in which it is noticeable that all scenes were recorded with sound, unlike the previous practice where certain scenes (mostly shot outdoors) were recorded without sound. The end of the 1960s marked the attainment of a high standard in the sound editing profession (and picture editing profession as well), making it possible to establish the Editing Department at the former Academy of Theatre Arts, where practical artistic class teachings were led by experienced film professionals with extensive knowledge and experience, capable of educating the next generation of filmmakers. However, due to limited spatial, material, and performance capabilities, the Editing Department did not offer specialization in the field of sound editing, which was only made available to students with the launch of the graduate study program in Sound Design (in the academic year 2007/2008). The soundscapes of Croatian feature-length fiction films up to the 1970s were defined by only a few sound editors (Lidija Jojić, Tea Brunšmid, Živan Cvitković). They distinguished themselves through their work, innate affinities, and the determination and patience to find solutions and methods suitable for each film, thereby advancing their profession while maintaining professional standards. Their work, as well as the work of film picture editors, represents an unfairly neglected area of research, research in film studies, and expert theses, and this work aims to partially correct this omission
Neuroprotective activity of cholinesterase reactivators in organophosphate poisoning
No full textKationski piridinijevi oksimi koriste se kao reaktivatori inhibiranih enzima acetilkolinesteraze (AChE) i butirilkolinesteraze (BChE) pri liječenju trovanja organofosfornim (OP) živčanim bojnim otrovima i pesticidima. Međutim, neučinkoviti su za reaktivaciju sinaptičke AChE u mozgu zbog otežanog prolaska kationa kroz krvno-moždanu barijeru, što može potaknuti neuroupalu i trajno oštetiti moždane funkcije. Cilj ovog istraživanja bio je ispitivanje neuroprotektivnog potencijala triju novosintetiziranih skupina oksima s obzirom na poboljšane fizikalno-kemijske karakteristike u odnosu na piridinijeve oksime. Od osam oksima kationske imidazolijeve skupine, 1,3-dibenzil-2-((hidroksiimino)metil)imidazolijev bromid pokazao se učinkovitim reaktivatorom fosfilirane BChE s kojom je kao pseudokatalitički par u ex vivo uvjetima unutar 5 minuta vratio 60 % enzimske aktivnosti, što ga čini izvrsnim kandidatom za razgradnju OP spojeva u cirkulaciji prije nego dođu do ciljnih tkiva. Također, tri zwitterionska acetamidna bis-oksima na modelu miša pokazala su bolji zaštitni indeks i manju akutnu toksičnost od standardnih oksima. Terapija jednim od bis-oksima vratila je oko 70 % aktivnosti inhibirane AChE u mozgu i značajno je smanjila ekspresiju neuroupalnih biljega astroglioze i mikroglioze. Analizirani bis-oksimi imaju kapacitet sprječavanja aktivacije neuroupalnih procesa i pokazuju perspektivna fizikalno-kemijska svojstva za razvoj poboljšane terapije u slučaju trovanja OP spojevima.Cationic pyridinium oximes are used as reactivators of inhibited acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) in the treatment of poisoning with organophosphorus (OP) nerve agents and pesticides. However, they are ineffective in reactivating synaptic AChE in the brain due to the difficulty of cation passage through the blood-brain barrier, which can induce neuroinflammation and permanently damage brain functions. The goal of this research was determining the neuroprotective potential of three newly synthesized oxime groups with regard to improved physicochemical characteristics compared to pyridinium oximes. Out of the eight cationic imidazolium oximes,
1,3-dibenzyl-2-((hydroxyimino)methyl)imidazolium bromide proved to be an effective ex vivo reactivator of phosphorylated BChE and as a pseudocatalytic pair it restored 60 % of the enzyme activity with a 10-fold excess cyclosarin, which makes it an excellent candidate for the degradation of OP compounds in the circulation before they reach the target tissues. Three zwitterionic acetamide bis-oximes showed a better protective index and less acute toxicity than standard oximes in a mouse model. Therapy with one of the bis- oximes restored about 70 % of the inhibited AChE in the brain and significantly reduced the expression of neuroinflammatory markers of astrogliosis and microgliosis. The analyzed bis- oximes have the capacity to prevent the activation of neuroinflammation and show promising physicochemical properties for the improvement of therapy in case of OP poisoning
Influence of the type of the reactants and reaction parameters on the synthesis of biodiesel fuels from higher alcohols
No full textIstraživanje i razvoj naprednih biogoriva motiviran je smanjenjem negativnog utjecaja na okoliš uzrokovanog višestoljetnom primjenom fosilnih goriva, a potaknut i od strane zakonskih regulativa Europske Unije koje potiču energetsku diverzifikaciju, dekarbonizaciju prometnog sektora te načela kružnog gospodarstva. Jedno od takvih biogoriva je i biodizel, koji se proizvodi transesterifikacijom triglicerida alkoholom, u prisutnosti katalizatora. Nakon pročišćavanja, moguće ga je namiješati s fosilnim gorivom te, ukoliko zadovolji norme za dizelsko (HRN EN 590) i biodizelsko (HRN EN 14214) gorivo, koristiti kao obnovljivi izvor energije u dizel motorima. U Republici Hrvatskoj dopušteno je namiješavanje biodizelskog s dizelskim gorivom do volumnog udjela od 7 % da bi se njihova mješavina i dalje deklarirala dizelskim gorivom. Biodizel je moguće s dizelskim gorivom namiješati i u višim volumnih udjelima, no u tom se slučaju radi o mješavinama dizelskog i biodizelskog goriva. S obzirom da se komercijalni biodizel u Europi najčešće proizvodi iz djelomično obnovljivog metanola, cilj ovog doktorskog rada bio je ispitati utjecaj vrste reaktanata i reakcijskih uvjeta na proces sinteze biodizela iz izomera različitih viših alkohola (od propanola do oktanola), koje je moguće kao bioalkohole fermentacijom u potpunosti proizvesti iz biomase. U prvom dijelu ovog doktorskog rada praćen je utjecaj reakcijskih uvjeta (temperature, vremena reakcije, molarnog omjera reaktanata te masenog udjela katalizatora) na iskorištenje reakcije transesterifikacije. Primjenom Box-Behnkenovog dizajna eksperimenta i metodologije odzivnih površina, analizirani su i optimirani sustavi u kojima je biodizel sintetiziran iz suncokretovog ulja i alkohola 1-propanola ili 1-oktanola, odnosno otpadnog ulja i sekundarnog alkohola 2-propanola, 2-butanola, 2-pentanola ili 2-oktanola, u prisutnosti kalijeva hidroksida (KOH), kao katalizatora. Dodatno, praćena je i ovisnost iskorištenja sinteze biodizela o spomenutim reakcijskim uvjetima, kemijskoj strukturi te molekulskoj masi reaktanata, u prisutnosti KOH, pri čemu su različite biosirovine bile suncokretovo, repičino, kokosovo, otpadno ulje te životinjska (svinjska) mast, koje su reagirane s 1-propanolom,
1-butanolom, izobutanolom, 1-pentanolom, izopentanolom, 1-heksanolom ili 2-heksanolom.
U drugom dijelu rada, veće šarže biodizela (metilnih, propilnih, butilnih, izobutilnih, pentilnih, heksilnih i oktilnih estera masnih kiselina) sintetizirane su iz otpadnog ulja u prisutnosti KOH, pri uvjetima najviših eksperimentalnih iskorištenja; pročišćene te namiješane u dvokomponentne i trokomponentne mješavine s neaditiviranim mineralnim dizelom i/ili odgovarajućim alkoholom. Provedena je analiza primjenskih svojstava priređenih uzoraka prema odgovarajućim normiranim metodama (gustoće, kinematičke viskoznosti, maglišta, točke filtrabilnosti, tecišta, mazivosti, simulirane destilacije), čije su vrijednosti uspoređene s onima propisanima normom za dizelsko gorivo HRN EN 590. Dodatno su uzorci analizirani metodama: diferencijalna pretražna kalorimetrija, mjerenje napetosti površine goniometrom i mjerenje koeficijenta trenja. Glavni rezultati su pokazali da su za iskorištenje ovih reakcijskih sustava značajni reakcijski uvjeti molarni omjer reaktanata i maseni udio katalizatora KOH, odnosno da se u promatranim sustavima, generalno najviša iskorištenja dobivaju korištenjem kokosovog ulja, a najniža korištenjem životinjske masti, kao biosirovine. Iskorištenja biodizela sintetiziranih iz ravnolančanih alkohola generalno su bila viša od onih sintetiziranih iz granatih, a porast molekulske mase granatih alkohola dovodi do daljnjeg sniženja iskorištenja. Karakterizacijom uzoraka utvrđeno je da dodatak biodizelskih goriva do 20 vol.% u mješavine s dizelom i/ili pripadajućim alkoholom rezultira porastom njihove gustoće, kinematičke viskoznosti i površinske napetosti, dok dodatak viših alkohola do 15 vol.% u odgovarajuće mješavine s dizelom i biodizelom rezultira smanjenjem njihove gustoće, kinematičke viskoznosti i površinske napetosti. Vrijednosti gustoća i kinematičkih viskoznosti za sve dvokomponentne mješavine dizel-biodizel (s do 20 vol.% biodizela) te trokomponentne mješavine dizel-biodizel-pripadajući alkohol (s do 15 vol.% biodizela) nalaze se unutar granica propisanih normom za dizelsko gorivo HRN EN 590. Nadalje, namiješavanjem biodizelskih goriva i/ili odgovarajućih alkohola s mineralnim dizelom nije došlo do narušavanja njegovih nisko-temperaturnih svojstava (maglišta, točke filtrabilnosti, tecišta). Reološkim mjerenjima utvrđeno je da dodatak heksilnih estera masnih kiselina neaditiviranom mineralnog dizelu u količini od 2,5 vol.% značajno poboljšava njegovu mazivost, dok promjena udjela ili vrste biodizela namiješanog s mineralnim dizelom nema značajnog utjecaja na svojstva podmazivanja dizelskog goriva. Naposljetku, uočeno je da su za destilaciju istog postotka predestiliranog, dodatkom pentilnih estera masnih kiselina od
20 vol.% mineralnom dizelu, potrebne više temperature nego u slučaju dodatka istog biodizela u udjelu od 10 vol.%. Diferencijalna pretražna kalorimetrija pokazala je da dvokomponentne i trokomponentne mješavine svih biodizela s mineralnim dizelom i/ili pripadajućim alkoholom imaju temperature početke i kraja kristalizacije slične vrijednostima onih neaditiviranog mineralnog dizela. Navedeno može poslužiti kako dodatni pokazatelj izostanka njihova negativnog djelovanja na niskotemperaturna svojstva dizelskog goriva.The research and development of advanced biofuels is motivated by the reduction of negative environmental impact caused with the use of fossil fuels throughout the centuries, and encouraged with the legal regulations of European Union, that promote energy diversification, decarbonization of the traffic sector, as well as the principles of circular economy. One of such biofuels is biodiesel, that is produced via alcohol transesterification of a certain feedstock, in the presence of a catalyst. Post purification, it is possible to blend it with fossil fuel, if it fulfills the requirements set by the diesel (HRN EN 590) and biodiesel (HRN EN 14214) standard, and use as a renewable source of energy in diesel engines.
In the Republic of Croatia it is allowed to blend up to 7 vol% of biodiesel with diesel fuel for their blend to still be declared as diesel fuel. It is possible to blend higher volume fractions of biodiesel fuel with diesel fuel, as well, however these are referred to as the diesel-biodiesel blends. Since the commercial European biodiesel is most commonly produced from partly renewable methanol, the goal of this doctoral thesis was to investigate the influence of the reactant type and the reaction conditions on the biodiesel synthesis from isomers of selected higher alcohols (from propanol to octanol), which can, as bioalcohols, be completely produced via fermentation from biomass. In the first part of this doctoral thesis, the influence of reaction conditions (temperature, reaction time, molar ratio of the reactants, and mass fraction of the catalyst) on the reaction conversion of the biodiesel systems, was studied. With the use of Design of Experiments by Box-Behnken and Response Surface Methodology, the biodiesel synthesis from either sunflower oil and alcohols 1-propanol or 1-octanol, or waste cooking oil and 2-propanol, 2-butanol, 2-pentanol, or 2-octanol, was analyzed and optimized, in the presence of a catalyst potassium hydroxide. Additionally, the dependence of the reaction conversion on the mentioned reaction conditions, the chemical structure, and the molar mass of the reactants, in the presence of potassium hydroxide, was studied, with the selected feedstock being sunflower oil, rapeseed oil, coconut oil, waste cooking oil, or animal fat, that reacted with 1-propanol, 1-butanol, isobutanol, 1-pentanol, isopentanol,
1-hexanol, or 2-hexanol. In the second part of the thesis, larger amounts of biodiesels (fatty acid methyl, propyl, butyl, isobutyl, pentyl, hexyl, and octyl esters) were synthesized from waste cooking oil, in the presence of KOH, at the conditions of the highest experimental conversions; purified, and blended into the binary and trinary blends with non-additivated mineral diesel and/or corresponding alcohol. The prepared samples underwent the application property analysis via corresponding standardized methods (density, kinematic viscosity, cloud point, cold filter plugging point, pour point, lubricity, simulated distillation),
the results of which were compared with the ones prescribed by the standard for diesel fuel HRN EN 590. Additionallly, samples were analyzed via instrumental analytical methods: differential scanning calorimetry, surface tension measurements via goniometer, and friction coefficient measurements. The main results showed that the most significant reaction conditions in the given systems were the molar ratio of the reactants, and the mass fraction of the catalyst KOH, and that in the selected systems experimentally the highest conversions were obtained using coconut oil, while the lowest using animal fat, as a feedstock.
The reaction conversions in the synthesis using straight-chain alcohols were generally higher than those with branched alcohols, and the increase in the molecular weight of branched alcohols further led to a decrease in the conversion. Sample characterization determined the addition of selected biodiesel fuels up to 20 vol% into the blends with mineral diesel and/or corresponding alcohol led to the increase in their density, kinematic viscosity, and surface tension, while the addition of the selected higher alcohol up to 15 vol% in the blends with diesel and biodiesel resulted in the reduction of their density, kinematic viscosity, and surface tension. Density and kinematic viscosity values of all the binary diesel-biodiesel (with up to 20 vol% of biodiesel), and trinary diesel-biodiesel-corresponding alcohol blends (with up to 15 vol% of biodiesel) were within the limits required by the standard for diesel fuel HRN EN 590. Furthermore, blending of selected biodiesels and/or corresponding alcohols with mineral diesel did not aggravate its analyzed low-temperature properties (cloud point, cold filter plugging point, pour point). Rheological measurements determined that the addition of fatty acid hexyl esters to non-additivated mineral diesel of just 2.5 vol% significantly improved its lubricity, whereas the change in the volume fraction or the type of biodiesel blended with mineral diesel did not have a significant influence on the diesel’s lubricating properties. Finally, it was observed that for the distillation of the same percentage of the sample, the higher temperatures were required with the addition of fatty acid pentyl esters of 20 vol% to mineral diesel, than with the addition of the same biodiesel in the volume fraction of 10 vol%. On the other hand, differential scanning calorimetry showed that the binary and trinary blends of all biodiesels with mineral diesel and/or corresponding alcohol had onset and peak crystallization temperature values close to the ones of non-additivated mineral diesel. This could serve as an additional indicator for the lack of their negative impact on the diesel’s low-temperature properties
RAZVOJ NETKANOG AGROTEKSTILA IZ PRIRODNIH I OBNOVLJIVIH IZVORA ZA PRIMJENU U MALČIRANJU
No full textOver the past decade, growing awareness of the environmental impact of consumer products has driven a shift toward sustainable materials. The trend extends to textiles, including agrotextiles, since agrotextiles are predominantly fossil-based and pose significant ecological challenges due to their disposal. The doctoral dissertation focuses on developing nonwoven fabrics made from natural and renewable sources for mulching applications. Nonwoven mulches are produced mechanically on the card and bonded by the needle-punching process. The dissertation is divided into two experiments. The first experiment evaluates the biodegradability, weed control and soil quality impact of nonwoven mulches made from viscose (CV), jute, hemp and polylactic acid (PLA) fibres, and mulch blends made from viscose (CV), jute and hemp fibres blended with PLA fibres in a ratio of 80:20 as a potential sustainable alternative to conventional low-density polyethylene (LDPE) agrofoil. The second experiment investigates the impact of the same nonwoven mulches on lettuce growth and yield, comparing them to a control field (bare soil) and conventional PE agrofoil. Field experiments revealed significant visual and morphological changes confirmed by SEM analysis and structural and mechanical changes in the nonwoven mulches during exposure due to field conditions. Field conditions during experiments affected the mass per unit area, thickness, air permeability, and tensile properties of mulches, where PLA mulches and mulch blends with PLA show superior stability over time. The molecular degradation of cellulose-based fibres was confirmed through FTIR and WAXD analyses. The PLA mulches demonstrated greater resilience to open field conditions. Nonwoven mulches enhance soil conditions by stabilising soil temperature and moisture, increasing organic carbon levels, and promoting microbial activity, often outperforming PE agrofoil. Weed suppression of nonwoven mulches was confirmed, where PLA-based mulches maintain effectiveness during an extended period of exposure, since the cellulose-based mulches, by degradation, lose weed suppression ability. In the lettuce cultivation, CV and jute blends with PLA outperformed PE agrofoil in productivity and nutrient content in lettuce and soil, highlighting their potential for sustainable agriculture. The results confirm that nonwoven mulches successfully suppress weed growth, are biodegradable without negatively impacting soil quality, and increase lettuce yield through their impact on the soil. This makes them a viable replacement for conventional PE agrofoil, where the possibility of their application significantly contributes to ecologically sustainable agricultural practices.Tijekom prošlog desetljeća, rastuća svjesnost o utjecaju proizvoda na okoliš potaknula je prelazak na održive proizvode. Trend obuhvaća i tekstil, uključujući agrotekstile, koji se uglavnom proizvode iz fosilnih izvora predstavljajući značajan ekološki izazov kod gospodarenja otpadom nakon upotrebe. Doktorska disertacija usmjerena je na razvoj netkanih tekstila proizvedenih od prirodnih vlakana te vlakana iz obnovljivih izvora za primjenu u malčiranju. Malčevi od netkanog tekstila proizvedeni su mehaničkim procesom na grebenaljci i učvršćeni postupkom iglanja. Disertacija je podijeljena u dva eksperimenta. Prvi eksperiment procjenjuje biorazgradljivost, učinak suzbijanja rasta korova i utjecaj na kvalitetu tla netkanih malčeva proizvedenih od vlakana viskoze (CV), jute, konoplje i polimliječne kiseline (PLA), te malčeva proizvedenih iz vlakana viskoze (CV), jute i konoplje u mješavini s PLA vlaknima u omjeru 80:20 kao potencijalnu održivu alternativu konvencionalnoj polietilenskoj agrofoliji niske gustoće (LDPE). Drugi eksperiment, istražuje utjecaj istih netkanih malčeva na rast salate i prinos, u usporedbi s kontrolnim poljem (neprekriveno tlo) i konvencionalnom PE agrofolijom. Istraživanja na polju otkrili su značajne vizualne, morfološke promjene potvrđene SEM analizom, te mehaničke i strukturne promjene netkanih malčeva tijekom izlaganja poljskim uvjetima. Uvjeti na polju tijekom istraživanja utjecali su na masu po jedinici površine, debljinu, propusnost zraka i vlačna svojstva netkanih malčeva. Malčevi proizvedeni iz PLA vlakana i u mješavinama s PLA vlaknima pokazuju bolju stabilnost tijekom vremena izlaganja. Molekularna razgradnja celuloznih vlakana potvrđena je FTIR i WAXD analizama, dok su PLA vlakna pokazala veću otpornost na vanjske uvjete polja. Netkani malčevi poboljšali su uvjete tla stabilizacijom temperature i vlage, povećanjem razine organskog ugljika i povećanjem aktivnosti mikroba u tlu, često nadmašujući PE agrofoliju. Potvrđeno je suzbijanje korova netkanim malčevima, pri čemu su malčevi proizvedeni u mješavinama s PLA vlaknima učinkovitiji tijekom duljeg razdoblja izloženosti, budući da malčevi na bazi celuloze razgradnjom gube sposobnost suzbijanja korova. Pri uzgoju salate,malčevi proizvedeni iz mješavina vlakana jute i PLA, te vlakana CV i PLA, nadmašili su PE agrofoliju u prinosu i sadržaju hranjivih tvari salate i tla, naglašavajući njihov potencijal za korištenje u održivoj poljoprivredi. Rezultati potvrđuju da netkani malčevi uspješno suzbijaju rast korova, biorazgradivi su bez negativnog utjecaja na kvalitetu tla i svojim djelovanjem na tlo povećvaju prinos salate. To ih čini održivom zamjenom konvencionalne PE agrofolije, a mogućnost njihove primjene značajnim doprinosom ekološki održivim poljoprivrednim praksama