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Synthesis of palladated azobenzenes and their application as catalysts for the Suzuki-Miyaura reaction in the solid state
No full textU ovoj je disertaciji prvi put u čvrstom stanju detaljno proučena Suzuki-Miyaurova reakcija, važna reakcija unakrsnog spajanja. Praćenje u realnom vremenu Ramanovom spektroskopijom in situ te spektroskopskim i difrakcijskim metodama ex situ omogućilo je analizu ključnih parametara reakcije s naglaskom na vrstu i količinu dodataka te su određeni čimbenici koji utječu na uspješnost reakcije u čvrstom stanju. Korištenjem strukturno različitih paladijevih katalizatora utvrđena je bolja katalitička aktivnost spojeva monomerne strukture s halogenidima i N-donornim ligandima. Detaljno je ispitano ponašanje fenilboronske kiseline u prisutnosti organskih baza pri čemu su strukturno okarakterizirani adukti trifenilboroksina i amina te im je ispitana stabilnost i sklonost vezanju amina različite bazičnosti. Razvijena je metoda za pripravu paladocikličkih spojeva aktivacijom veze ugljik-vodik u čvrstom stanju potpomognutom Brønstedovim kiselinama na primjeru derivata azobenzena pri čemu je uočen značajan utjecaj primijenjenih kiselina na brzinu i uspješnost reakcije. Priređeni paladociklički spojevi azobenzena uspješno su katalizirali Suzuki-Miyaurovu i Sonogashirinu reakciju u čvrstom stanju.This thesis presents the first comprehensive study of the solid-state Suzuki-Miyaura reaction. Real-time in-situ monitoring using Raman spectroscopy and ex-situ spectroscopic and diffraction techniques enabled the investigation of key reaction parameters. Varying the type and amount of additives revealed critical factors that govern the efficiency of the solid-state reaction. The use of structurally diverse palladium catalysts showed that monomeric complexes bearing halide anions and nitrogen-donor ligands exhibit superior catalytic activity. The solid- state reactivity of phenylboronic acid in the presence of organic bases was examined. Adducts formed between triphenylboroxine and amines were structurally characterised, and their stability was found to correlate with the basicity of the bound amine. A solid-state method for preparing palladated azobenzenes via Brønsted acid-promoted carbon-hydrogen bond activation was developed, revealing that the choice of acid significantly affects both the rate and the outcome of the reaction. The prepared azobenzene palladacycles were successfully applied as catalysts for the solid-state Suzuki-Miyaura and Sonogashira reactions
Early social capital and personal capital as determinants of subjective career success of doctors of sciences at universities in the Republic of Croatia
No full textDoktorski rad pod nazivom „Rani socijalni kapital i osobni kapital kao odrednice subjektivnoga
karijernog uspjeha doktora znanosti na sveučilištima u Republici Hrvatskoj“, uz pregled
literature i operacionalizaciju pojmova te pregled dosadašnjih istraživanja, daje rezultate
istraživanja koje je za cilj imalo istražiti postoje li razlike: u (1) u ranom socijalnom kapitalu s
obzirom na socio-demografske karakteristike i znanstveno područje, (2) u percepciji
emocionalne inteligencije s obzirom na socio-demografske karakteristike i znanstveno
područje, (3) u povezanosti između percepcije emocionalne inteligencije i subjektivnog
karijernog uspjeha s obzirom na socio-demografske karakteristike, (4) u povezanosti između
petfaktorskog modela ličnosti i subjektivnog karijernog uspjeha s obzirom na sociodemografske karakteristike, (5) u povezanosti između ranog socijalnog kapitala i subjektivnog
karijernog uspjeha s obzirom na socio-demografske karakteristike, (6) u povezanosti između
ranog socijalnog kapitala i subjektivnog karijernog uspjeha s obzirom na percepciju
emocionalne inteligencije i petfaktorski model ličnosti kod doktora znanosti na sveučilištima u
Hrvatskoj. Populacija istraživanja su doktori znanosti koji rade na sveučilištima u Republici
Hrvatskoj budući da je objektivan uspjeh u ovom radu definiran kao dostignuće najvišeg stupnja
obrazovanja. Stoga, cilj je istražiti subjektivni uspjeh objektivno uspješnih ljudi te čimbenike
koji su povezani s njime. Istraživanje je provedeno metodom ankete na sveučilištima u
Republici Hrvatskoj, na uzorku od 447 sudionika. Rezultati su pokazali kako postoji statistički
značajna razlika u ranom socijalnom kapitalu kada govorimo o mjestu rođenja i ekonomskom
statusu u djetinjstvu, dok se rani socijalni kapital ne razlikuje s obzirom druge sociodemografske karakteristike. Analiza je također pokazala razlike u emocionalnoj inteligenciji
između znanstvenika u STEM i društveno-humanističkom području, dok prema drugim
karakteristikama nema razlika. Rezultati su pokazali kako ne postoji statistički značajna
povezanost između ranog socijalnog kapitala i subjektivnog karijernog uspjeha, ali postoji
povezanost kod nekih dimenzija emocionalne inteligencije i subjektivnog karijernog uspjeha
odnosno kod nekih crta ličnosti i subjektivnog karijernog uspjeha. Socio-demografske
karakteristike uglavnom se nisu pokazale kao značajni moderatori značajnih povezanosti. Ovo
istraživanje ima znanstveni doprinos u definiranju, operacionalizaciji i mjerenju ranog
socijalnog kapitala, te njegovog suodnosa s emocionalnom inteligencijom i subjektivnim
karijernim uspjehom ali socio-demografskim karakteristikama doktora znanosti u Hrvatskoj.
Također, istraživanje ima snažne praktične implikacije u kontekstu razumijevanja znanstvenog
sustava, karijernog uspjeha, unapređenja radnih uvjeta i posljedično, zadovoljstva poslom
doktora znanosti na hrvatskim sveučilištimaThe doctoral thesis entitled "Early social capital and personal capital as determinants of the
subjective career success of PhDs at universities in the Republic of Croatia", along with a
unique review of the literature and operationalization of terms and an overview of previous
research, provides the results of research aimed at investigating whether there are differences:
in (1) in early social capital with regard to socio-demographic characteristics and scientific
field, (2) in emotional intelligence with regard to socio-demographic characteristics and
scientific field, (3) in the connection between emotional intelligence and subjective career
success with regard to socio-demographic characteristics, (4) in the connection between the
five-factor model of personality and subjective career success with regard to socio-demographic
characteristics, (5) in the connection between early social capital and subjective career success
with regard to socio- demographic characteristics, (6) in the connection between early social
capital and subjective career success with regard to emotional intelligence and the five-factor
model of personality among PhDs at universities in Croatia. The research population is doctors
of science who work at universities in the Republic of Croatia, since objective success in this
paper is defined as the achievement of the highest level of education. Therefore, the goal is to
investigate the subjective success of objectively successful people and the factors associated
with it. The research was conducted using the survey method at universities in the Republic of
Croatia, on a sample of 447 participants. The results showed that there is a statistically
significant difference in early social capital when we talk about place of birth and economic
status in childhood, while early social capital does not differ with regard to other sociodemographic characteristics. The analysis also showed differences in emotional intelligence
between scientists in STEM and social-humanities fields, while there were no differences
according to other characteristics. The results showed that there is no statistically significant
connection between early social capital and subjective career success, but there is a connection
with some dimensions of emotional intelligence and subjective career success, that is, with
some personality traits and subjective career success. Socio-demographic characteristics mostly
did not prove to be significant moderators of significant associations. This research has a strong
scientific contribution in terms of defining, operationalizing and measuring early social capital,
and its correlation with emotional intelligence and subjective career success, as well as sociodemographic characteristics of PhDs in Croatia. Also, the research has strong practical
implications in the context of understanding the scientific system, career success, improvement
of working conditions and, consequently, job satisfaction of PhDs at Croatian universities
Adaptivno upravljanje numeričkim mrežama za računalno učinkovite simulacije velikih vrtloga : doktorski rad
No full textComputational fluid dynamics simulations often involve a trade-off between accuracy and computational cost, particularly when modelling complex flows with localised phenomena across varying scales. This trade-off becomes especially pronounced in high-fidelity simulations, which require fine grid resolution to capture intricate flow structures. Maintaining such resolution across the entire domain can, however, be computationally prohibitive. Adaptive mesh refinement is a promising methodological alternative that dynamically refines the grid in regions requiring higher accuracy and coarsens it in others. Still, its application for large eddy simulation is challenging since changes in grid resolution can induce instabilities, affect numerical dissipation, and ultimately compromise accuracy. This thesis aims to address these limitations by developing and validating a computationally efficient adaptive mesh refinement strategy tailored for large eddy simulation within the OpenFOAM 10 framework. The central hypothesis is that an effective and physically grounded refinement criterion can be defined to guide mesh adaptation efficiently. To implement the envisioned strategy, several code contributions have been made. First, native mesh refinement capabilities were extended to handle two-dimensional problems. Second, new classes were developed for two-dimensional and three-dimensional adaptive mesh refinement, enabling refinement decisions based on logical combinations of multiple criteria, including scalar fields and geometric constraints. Third, to address parallel performance concerns, two new load balancing classes were implemented. These distributors rely on direct measurements to assess load imbalance and trigger mesh redistribution. A core contribution is the formulation of a composite refinement criterion tailored specifically for large eddy simulations. The criterion combines the vortex identification method with a measure of local mesh resolution relative to the turbulent Taylor microscale. This ensures that coherent vortical structures are captured and the mesh is sufficiently fine to resolve the relevant turbulent scales locally. Validation was performed systematically on a selected set of test cases. These confirmed that the implementation functions as intended and demonstrated the potential of multi-criteria adaptive mesh refinement. The composite refinement criterion was applied to benchmark large eddy simulation cases, yielding comparable or superior accuracy relative to simulations using a conventional grid generation approach. The load balancing algorithms were also evaluated, demonstrating improved parallel efficiency and reduced simulation times. The results suggest that the proposed approach effectively balances accuracy and computational cost for large eddy simulations. By integrating targeted refinement criteria with performance-aware load balancing, the adaptive mesh refinement strategy is able to provide high-fidelity numerical results with significantly lower computational demands, making it a
practical solution for complex research and industrial problems.Simulacije u domeni računalne dinamike fluida često uključuju kompromis između točnosti i računalnog troška, osobito prilikom modeliranja složenih strujanja s lokaliziranim pojavama različitih skala. Taj kompromis postaje posebno izražen u simulacijama koje zahtijevaju finu razlučivost numeričke mreže, kako bi se obuhvatile složene strukture strujanja. Ipak, održavanje takve razlučivosti na razini cjelokupne domene može biti računalno preskupo. Adaptivno upravljanje predstavlja obećavajuću metodološku alternativu koja dinamički modificira numeričke mreže u područjima koja zahtijevaju veću točnost, dok ih u drugim područjima razrjeđuje. Međutim, primjena ove metode u simulacijama velikih vrtloga predstavlja izazov jer promjene u razlučivosti mreže mogu izazvati nestabilnosti, utjecati na numeričku disipaciju i na kraju utjecati na točnost. Ova disertacija ima za cilj ponuditi rješenje za navedena ograničenja razvijanjem i validacijom računalno učinkovite strategije adaptivnog upravljanja, prilagođene simulacijama velikih vrtloga unutar OpenFOAM 10. Središnja hipoteza jest da se može definirati učinkovit i fizikalno utemeljen kriterij za upravljanje mrežom, koji će učinkovito usmjeravati adaptaciju mreže. Za provedbu zamišljene strategije ostvareni su brojni programski doprinosi. Prvo, izvorne mogućnosti proširene su kako bi podržale dvodimenzionalne probleme. Drugo, razvijene su nove klase za dvodimenzionalno i trodimenzionalno adaptivno upravljanje, omogućujući donošenje odluka o upravljanju temeljenih na logičkim kombinacijama više kriterija, poput skalarnih polja i geometrijskih ograničenja. Treće, kako bi se riješio problem učinkovitosti pri paralelnom izvođenju, implementirane su dvije nove klase za uravnoteženje opterećenja. Spomenute klase oslanjaju se na izravna mjerenja resursa za procjenu neuravnoteženosti i iniciranje redistribucije mreže. Ključni doprinos je formulacija kompozitnog kriterija upravljanja posebno prilagođenog za simulacije velikih vrtloga. Kriterij kombinira metodu identifikacije vrtloga s mjerom lokalne razlučivosti mreže u odnosu na turbulentnu Taylorovu mikroskalu. Na taj se način osigurava da su koherentne vrtložne strukture obuhvaćene te da je mreža dovoljno fina za lokalno razlučivanje relevantnih turbulentnih skala. Validacija je provedena sustavno na odabranom skupu testnih sluˇ cajeva. Na temelju dobivenih rezultata utvrđeno je da implementacija djeluje prema očekivanjima te je potvrđen potencijal kompozitnog kriterija za upravljanje numeričkim mrežama. Kompozitni kriterij primijenjen je na referentne slučajeve simulacija velikih vrtloga, pri čemu su ostvareni rezultati pokazali usporedivu ili veću točnost u odnosu na simulacije koje koriste konvencionalni pristup generiranju mreže. Algoritmi za uravnoteženje opterećenja također su evaluirani, pri čemu je zabilježena poboljšana paralelna učinkovitost i smanjenje ukupnih proračunskih vremena. Ostvareni rezultati sugeriraju da je moguće definirati kompozitni kriterij koji, u kombinaciji s algoritmima za uravnoteženje opterećenja, omogućuje postizanje numeričkih rezultata visoke točnosti uz znatno niže računalne zahtjeve, čime se potvrđuje praktična primjenjivost predložene metodologije u složenim istraživačkim i industrijskim problemima
Position and influence of the Federation of Associations of Combatants of National Liberation War in Croatia during the 1970s and 1980s on the examples of Labin and Sisak municipalities
No full textPartizanski su ratni veterani u socijalističkoj Jugoslaviji imali istaknuto mjesto u procesu izgradnje države i za današnja poimanja neuobičajeno velik utjecaj na politiku i društvo koji do sad nije bio predmetom cjelovitog historiografskog istraživanja. Dosadašnja su se istraživanja uglavnom fokusirala na ulogu partizanskih boraca u oblikovanju i promicanju kulture sjećanja vezane uz Narodnooslobodilački rat, zanemarujući ostale aspekte njihovoga djelovanja o kojima svjedoče brojni pisani izvori. Okupljeni u vlastitu društveno-političku organizaciju pod nazivom Savez udruženja boraca Narodnooslobodilačkog rata (SUBNOR), borci su imali svoje ustavom propisane društvene zadatke, politikom i Programom Saveza komunista Jugoslavije utvrđene dužnosti te obveze socijalnog zbrinjavanja svojih članova. Rad na transmisiji partijske politike, ideologizaciji društva, mobilizaciji građana, snaženju zajedništva i patriotizma nadilazio je tipične okvire veteranske nadležnosti, a njihovo je mjesto u društvu još dugo vremena nakon rata bilo zapaženo. Namjera je ovog istraživanja pružiti višedimenzionalnu analizu djelovanja SUBNOR-a u Hrvatskoj s fokusom na sedamdesete i osamdesete kao godine u kojima se samoupravni socijalizam, teritorijalno-administrativna decentralizacija, podruštvljavanje i deetatizacija manifestiraju u svome najrazvijenijem obliku. Prva istraživačka hipoteza sugerira da su navedene promjene potaknule jačanje aktivizma u SUBNOR-u, snažniju povezanost s drugim društvenim strukturama i osuvremenjivanje brojnih aktivnosti s ciljem prilagodbe aktualnim društvenim promjenama, što je organizaciji donijelo produljeni utjecaj na društvo i politiku. Pod drugom je pretpostavkom reforma federacije premjestila težište aktivnosti boračke organizacije na lokalnu razinu gdje su se potom proklamirani ideali i politike različito primjenjivali u praksi. Fokus se rada, osim na republičkoj i saveznoj razini, smješta u dvije odabrane općine – Labin i Sisak, koje kao studije slučaja ocrtavaju fenomen položaja i utjecaja boraca u vlastitim kontekstima. Uz analizu odabranih arhivskih i novinskih izvora te onodobne i suvremene relevantne literature, mikrohistorijski se pristup prožima s republičkim i saveznim makropovijesnim okvirom.Partisan war veterans in socialist Yugoslavia had a prominent place in the process of building the state and, by today's standards, had an unusually large influence on politics and society. Their position and influence, especially in the society of late socialism, have not been the subject of comprehensive historiographical research until now. Previous works mainly focused on the role of partisan veterans in shaping and promoting the culture of memory related to the National Liberation War (NLW) in Yugoslavia, neglecting other aspects of their activities, as evidenced by numerous archival sources. Gathered in their own socio-political organization called the Federation of Veterans' Associations of National Liberation War (SUBNOR), the veterans had their social tasks determined by the constitution, various duties stipulated by the politics and the Program of the League of Communists of Yugoslavia and obligation to assist in the provision of social welfare to its members. The work on transmission of Party policy, ideologization of society, mobilization of citizens, strengthening of unity and patriotism went beyond the typical framework of veteran competence, and their place in society was prominent for a long time after the war.
The sole purpose of this research is to provide a multidimensional analysis of the activities of SUBNOR in Croatia with a focus on the seventies and eighties as the years in which self-managed socialism, territorial-administrative decentralization, fading and withering away of the state, manifest in their most developed form. The first research hypothesis suggests that the aforementioned changes encouraged the strengthening of activism in SUBNOR, a stronger connection with other social structures and the modernization of numerous activities with the aim of adapting to current social changes, which brought the organization a long-lasting impact on society and politics. The second hypothesis deals with the fact that the reform of the federation moved the center of gravity of the veterans' organization's activities to the local level, where the proclaimed ideals and policies were then applied differently in practice. The focus of the SUBNOR's work, apart from the republican and federal levels, is placed in two selected municipalities – Labin and Sisak, which as case studies outline the phenomenon of the position and influence of veterans in their own contexts. Along with the analysis of selected archival sources and periodicals (newspapers and magazines) and contemporary relevant literature, the micro historical approach is interwoven with the republican and federal macro historical framework.
SUBNOR was founded in September 1947 as a voluntary socio-political organization gathering partisan veterans, participants of the National Liberation Movement (NLM), war invalids, former concentration camp prisoners, internees, deportees, and political prisoners on the side of NLM, families of the fallen fighters and the victims of fascist terror, and certain categories of pre-war revolutionaries and participants of the resistance movement in the world. Along with the committees formed according to the territorial principle, from the smallest, local, municipal, and inter-municipal organizations to republican and provincial committees and the Federal Committee, which managed the work of the organization at the level of Yugoslavia, the veterans' organization was present in almost every corner of the Yugoslav federation. It gathered approximately one million members with diverse experiences of participation in NLW and pre-war revolutionary events. SUBNOR was formed with the aim of popularizing the achievements of the NLW and the revolution, as well as to support the building and shaping of a socialist society and the social wellbeing of the partisan generation. The portfolio of its activities, from various jobs within political and social activities, international veterans' cooperation, to raising the civil defense readiness and patriotic and ideological shaping of children and young people, clearly reflected degree of involvement of veterans in the public and social life of Yugoslavia. It was an integral part of the umbrella socio-political organization – the Socialist Alliance of the Working People, its own work program was based on the program and policy of the League of Communists of Yugoslavia, and veterans' rights were constitutionally guaranteed.
The 1960s were a turning point in the work and activity of SUBNOR, just as they proved to be a turning point in the case of the political, economic, and cultural development of the self-managed socialist Yugoslavia. In that decade, a large part of the war generation retires from leadership positions, while on the other hand, the key processes of decentralization and strengthening of local committees are starting to happen. Soon followed the politicization of the entire membership and socialization of numerous SUBNOR activities that enabled the organization to turn towards everyday politics and social relations instead of sticking strictly to the socioeconomic issues of veterans. Changed responsibilities and work priorities will be most recognized in veterans' participation in social self-management, modernization of commemorative practices, more intensive cooperation with other organizations and institutions, greater independence in leading and developing international veteran cooperation, as well as in increased opportunities for veterans' welfare at the local level in relation to republican and federal welfare provisions. Like never before, the position and influence of the combatants will depend on political, social, and economic trends in the municipality, on the favor of local political elites and bureaucratic structures, but also on the activism of prominent individuals of the organization.
Due to all the above mentioned, veteran organizations in Labin and Sisak, created on similar foundations of strong traditions of the labor and revolutionary movement, i.e., anti-fascist resistance, make meaningful case studies in the context of activism and the culture of remembrance of NLW. In these two cities, as important symbolic centers of archetypal workers' resistance and revolutionary mass uprisings, there was a lot of room for the growth of the reputation and influence of partisan veterans in post-war society compared to some other environments. The imperative to preserve and affirm the memory of NLW for a long time encouraged the creation of specific local memoryscapes. Revolutionary enthusiasm had to be translated into examples of responsible, ideologically correct, and consistent behavior of every individual in society. Industrial production, as a key initiator of urban development, modernization, and improvement of the standards of Labin and Sisak society, formed an important context for the social care of the local veteran population thanks to the economic possibilities of the municipality. The focus of veterans could thus be more easily moved away from veterans' health and socioeconomic issues, in contrast to, for example, rural and underdeveloped areas where the solution of socioeconomic issues was not standardized enough but turned into a source of veteran dissatisfaction. With their historical differences and particularities, these two environments bear witness to numerous phenomena concerning local politics, interpersonal relations, issues of identity, interrelationships of local power structures, cooperation and connections at the international level, and issues of social security and regime stability. From open criticism and self-criticism, political pressure, coping and lobbying, to networking with young people and sensitizing citizens to their own issues and interests, Labin and Sisak veterans' organizations reveal how socialism functioned on a microlevel.
The purpose of this dissertation is to answer the question on what the analysis of the activities of the SUBNOR municipal committees in Labin and Sisak can say about the role of the partisan generation in the construction of socialism. What characterized the relationship between veterans, the communist state and socialist society? What was the role of the mostly retired partisan generation in the system of fully developed self-managed socialism? How did the veterans live thirty or forty years after the war? The thesis, from the perspective of social history and microhistory, first deals with the definition of the partisan veteran population, their war experience, and the context of the formation of SUBNOR as a specific mass organization. It then provides a chronological overview of the organizations' activities at the federal and republic level, with a review of the issue of membership, assumed roles and tasks of socio-political organizations in the society of self-managed socialism. In the following part of the dissertation, the histories of the activities of the Labin and Sisak veterans' organizations are presented, along with the analysis of key elements in the organizations' activities during the period of late socialism, that is activism within the framework of social self-management, preservation and popularization of war memories, welfare and social care of members, SUBNOR's international cooperation and its role in the People's Defense and Social Self-Defense system in Yugoslavia. The aforementioned activities are problematized with the help of various examples and sources from the local level. Archival sources collected in the Archives of Yugoslavia in Belgrade, the Croatian State Archives in Zagreb, the State Archives of Sisak and the State Archives of Rijeka, as well as records from the archives of the Anti-fascist association in Labin and the Public Museum of Labin, were used for this purpose. Specialized veteran magazines and local newspapers of the time were indispensable in this regard. Their stories and details contributed significantly to the understanding of SUBNOR's true position and impact in Croatia. As a result, there is a need for a more nuanced understanding of the interaction between veterans, the state and society in socialist Yugoslavia, as well as a broader consideration of the peculiarities and functioning of socialism at the local level over the last two decades of its existence
Judgment as the establishment of consensus in the theory of understanding
No full textIdeja je istražiti pojam usuglašavanja kao polazišnu točku prosudbe, a prosudbu kao postupak uspostave konsenzusa analizirati, naglašavajući značaj i relevantnost refleksivne prosudbe kod Kanta u pogledu svrhovitosti. S obzirom na relativističku dimenziju prosudbe, potrebno je detaljno analizirati sve moguće odrednice plauzibilnost metodološkog prosuđivanja što bi u središte ponovo vratilo svojevrstan ideal objektivnosti koji je napušten zbog relativizacije kantovske apriornosti. Zbog toga je u procesu razumijevanja, objašnjenja i interpretacije znanstvenih teorija relevantnost prosudbe važan čimbenik na temelju kojeg je dalje moguća uspostava konsenzusa u argumentaciji znanstvene i akademske zajednice. Cilj je pronaći vjerodostojnu polazišnu točku, odnosno doći do legitimacije konsenzusa znanstvene zajednice i postaviti ga kao ispravan put prema znanstvenoj metodologiji, pri čemu se velike nade polažu u Kantov pojam sensus communisa.The idea is to explore the concept of agreement as a starting point of judgment, and to analyze judgment as a process of establishing consensus, emphasizing the importance and relevance of reflective judgment in Kant. With regard to the relativistic dimension of judgment, it is necessary to analyze in detail all possible determinants of the credibility of methodological judgment, which would return to the center some kind of ideal of objectivity that was abandoned due to the relativization of Kantian a priori. For this reason, in the process of understanding, explaining and interpreting scientific theories, the relevance of the judgment is an important factor on the basis of which it is possible to establish a consensus in the argumentation of the scientific and academic community. The goal is to find a credible starting point, that is, to legitimize the consensus of the scientific community and set it as the correct path towards scientific methodology, with great hopes placed in Kant's notion of sensus communis
The sialylation degree effect of alpha-1-acid glycoprotein on the equilibrium binding affinities of chosen drugs
No full textPrema hipotezi slobodnog lijeka, samo nevezana frakcija lijeka može ostvariti farmakološki ili toksični učinak. Vezanje lijekova na proteine plazme, posebno humani serumski albumin (HSA) i alfa-1-kiseli glikoprotein (AAG), značajno utječe na njihova farmakokinetička svojstva, poput klirensa i volumena distribucije. Osim što koncentracija AAG-a u plazmi raste tijekom bolesti, uočene su i promjene u njegovoj glikanskoj strukturi. Smatra se da, osim promjene koncentracije, i stupanj sijalinizacije AAG-a utječe na ravnotežni afinitet vezanja lijekova te time i na količinu slobodnog lijeka, što posljedično može utjecati na farmakokinetičke parametre. Cilj ovog rada bio je odrediti utjecaj stupnja sijalinizacije AAG-a na ravnotežni afinitet vezanja odabranih lijekova te simulirati utjecaj na koncentraciju slobodnog lijeka u plazmi. Desijalinizacija AAG-a provedena je korištenjem komercijalno dostupnih sijalidaza, a uspješnost procesa potvrđena je N-glikanskom analizom i kromatofokusiranjem. Molarni apsorpcijski koeficijenti nativnog i desijaliniziranog AAG-a određeni su Edelhochovom metodom, pri čemu je zaključeno da desijalinizacija ne mijenja molarni apsorpcijski koeficijent AAG-a. Utjecaj desijalinizacije na ravnotežni afinitet vezanja odabranih lijekova istražen je mikroskalarnom termoforezom, pri čemu je uočeno da desijalinizacija može povećati, smanjiti ili ne mijenjati ravnotežni afinitet vezanja, ovisno o lijeku. Simulacijama slobodnog lijeka u plazmi zaključeno je da stupanj sijalinizacije može utjecati na koncentraciju slobodnog lijeka, ali samo za lijekove koji pokazuju viši afinitet vezanja za AAG nego za HSA. Eksperimentima polarizacije fluorescencije pokazano je da ravnotežni afinitet vezanja dipiridamola na AAG ovisi o stupnju sijalinizacije, pri čemu parcijalna desijalinizacija rezultira vrijednostima afiniteta između nativnog i potpuno desijaliniziranog AAG-a. Uzrok ovisnosti ravnotežnih afiniteta vezanja lijekova o stupnju sijalinizacije pripisuje se promjeni konformacije AAG-a, što je potvrđeno diferencijalnom skenirajućom fluorimetrijom.According to the free drug hypothesis, only the unbound fraction of a drug can exert pharmacological or toxic effects. Drug binding to plasma proteins, particularly to human serum albumin (HSA) and alpha-1-acid glycoprotein (AAG), significantly affects their pharmacokinetic properties, such as clearance and volume of distribution. In addition to the increase in plasma AAG concentration during disease, changes in its glycan structure have also been observed. It is considered that, beyond changes in concentration, the degree of AAG sialylation influences the equilibrium binding affinity of drugs, thereby affecting the amount of free drug, which can subsequently impact pharmacokinetic parameters. The aim of this study was to determine the effect of AAG sialylation degree on the equilibrium binding affinity of selected drugs and to simulate its impact on the free drug concentration in plasma. Desialylation of AAG was performed using commercially available sialidases, and the efficiency of the process was confirmed by N-glycan analysis and chromatofocusing. The molar absorption coefficients of native and desialylated AAG were determined using the Edelhoch method, and it was concluded that desialylation does not affect the molar absorption coefficient of AAG. The effect of desialylation on the equilibrium binding affinity of selected drugs was investigated using microscale thermophoresis, where it was observed that desialylation can either increase, decrease, or have no effect on the equilibrium binding affinity, depending on the drug. Simulations of free drug concentration in plasma suggested that the degree of sialylation could affect the free drug concentration, but only for drugs exhibiting a higher binding affinity for AAG than for HSA. Fluorescence polarization experiments demonstrated that the equilibrium binding affinity of dipyridamole to AAG depends on the degree of sialylation, with partial desialylation resulting in binding affinities intermediate between those of native and fully desialylated AAG. The dependence of drug binding affinities on the degree of AAG sialylation is attributed to conformational changes induced by desialylation, as confirmed by differential scanning fluorimetry
The impact of invasive alien amphipods (Crustacea, Amphipoda) on macroinvertebrate community and leaf litter decomposition in large rivers
No full textInvazivne vrste su među najvažnijim uzrocima smanjivanja bioraznolikosti u slatkovodnim
ekosustavima. Rakovi iz nadreda Peracarida (redovi Amphipoda, Isopoda i Mysida) su skupina s
brojnim invazivnim vrstama. Prijašnjim istraživanjima, u velikim rijekama Hrvatske (Dunav, Sava,
Drava, Mura) zabilježeno je 13 stranih vrsta perakaridnih rakova, no malo se zna o njihovom
utjecaju na makrozoobentos, odnosu s abiotičkim čimbenicima te utjecaju na razgradnju listinca.
Ciljevi ovog rada obuhvatili su doprinos invazivnih stranih vrsta rakušaca biokontaminaciji
makrozoobentosa, njihov odnos s abiotičkim čimbenicima vode te utjecaj invazivnog rakušca
Dikerogammarus villosus na autohtone perakaridne rakove i razgradnju listinca. Strani perakaridni
rakovi dominiraju brojnošću jedinki te značajno doprinose biokontaminaciji istraživanih rijeka.
Iako se smatra da su otporni na onečišćenje vode, veće gustoće ovih rakova zabilježene su na
postajama s manjim onečišćenjem i višim vrijednostima bioloških metrika. Za utjecaj rakušca D.
villosus na razgradnju listinca dobiveni su oprečni rezultati koji pokazuju da njegov utjecaj ovisi o
okolnostima i sastavu zajednica usitnjivača. Uzvodno širenje ove vrste praćeno je smanjenjem
gustoće autohtonih perakaridnih rakova, osobito na šljunkovito-valutičastom supstratu pri čemu
nije zabilježen negativan utjecaj na fekunditet autohtonih rakušaca.Invasive species highly contribute to freshwater biodiversity loss. Peracarid crustaceans, the orders
Amphipoda, Isopoda, and Mysida consist of many invasive alien species. In Croatian large rivers
(Danube, Sava, Drava, Mura), 13 alien peracarid species have been recorded in previous studies,
yet little is known about their impact on aquatic macroinvertebrate communities, their relationship
with physico-chemical water parameters, and their influence on leaf litter decomposition. The
objectives of this work were to investigate their contribution to the biocontamination of
macrozoobenthos in large rivers, their relationship with abiotic factors, and the effects of the
invasive amphipod Dikerogammarus villosus on native peracarids and leaf litter decomposition.
Alien peracarids were abundant in studied rivers, contributing significantly to the biocontamination
of the rivers studied. Although assumed to be resistant to pollution, they exhibited higher
population densities at sites with higher values of biological metrics with lower level of pollution.
Conflicting results were obtained regarding the effects of D. villosus on decomposition rates of leaf
litter, as they depended on the circumstances and abundance of native shredders. The invasion of
D. villosus was accompanied by a decrease in population densities of native peracarids, especially
on stony substrates, while no negative effects of this invasive amphipod species on fecundity of
native amphipods were detected
The effect of inflammation on apoptotic cell death after ischemic lesion of the mouse brain
No full textPostishemijska upala značajan je faktor u razvoju ozljede nakon moždanog udara, a TLR2 receptor jedan je od njezinih glavnih medijatora. Glavni cilj ovog doktorata bio je odrediti utjecaj upale posredovane TLR2 receptorom na apoptozu u ishemijskom okolišu.
Utjecaj TLR2 receptora istražen je na modelu ishemijskog oštećenja mišjeg mozga u životinja s normalnim (CAG-luc) i onih s onemogućenim Tlr2 genom (CAG-luc-Tlr2-/-). Oba soja ubikvitarno su izražavala luciferazni transgen. Razmjer apoptoze pratio se bioluminiscencijom zatočenim Z-DEVD-aminoluciferinom koji se cijepa i postaje bioluminiscentno aktivan nakon interakcije s pocijepanom kaspazom-3. Ishemijska ozljeda bila je uzrokovana okluzijom srednje moždane arterije, a njena progresija praćen je magnetskom rezonancom. Stanična smrt je potvrđena metodama imunofluorescencije pocijepanom kaspazom-3, protočne citometrije aneksinom-V i TUNEL esejom. Funkcionalno oštećenje izmjereno je testom neurološkog deficita.
Zatočeni Z-DEVD-aminoluciferin validiran je i procijenjen kao adekvatan supstrat za praćenje apoptoze. Longitudinalno in vivo mjerenje apoptoze izazovno je te zahtijeva kvalitetnu validaciju i normalizaciju. Nije bilo ukupne razlike u apoptozi između sojeva, ali u nedostatku TLR2 receptora postojao je izraženiji mehanizam nekroze. U akutnom periodu, CAG-luc- Tlr2-/- miševi bolje su preživljavali od CAG-luc miševa, dok u kroničnom periodu nije bilo razlike u preživljenju. Ipak, magnetna rezonanca je pokazala kako su CAG-luc-Tlr2-/- miševi su u kroničnom periodu izgubili više tkiva ipsilateralne hemisfere od CAG-luc miševa. Stoga, iako smanjena upala u akutnom periodu može biti protektivna, dugoročno narušava oporavak.Postischemic inflammation is a significant contributor to ischemic injury development. The TLR2 receptor is one of its main mediators. The main aim of this thesis was to determine the effect of TLR2-mediated inflammation on apoptotic cell death in the ischemic environment.
The effect of TLR2 was investigated on the ischemic injury model in animals with normal Tlr2 (CAG-luc) and those with knock-out Tlr2 gene (CAG-luc-Tlr2-/-). Both strains expressed the firefly luciferase transgene ubiquitously. The scope of apoptosis was determined by the utilization of bioluminescence imaging with caged Z-DEVD-aminoluciferin, which becomes available for the bioluminescence reaction after cleavage with activated caspase-3. Middle cerebral artery occlusion was performed to produce the ischemic injury. Its progression was followed with magnetic resonance imaging. Cell death was further confirmed using immunofluorescence with activated caspase-3, flow cytometry with annexin-V and the TUNEL assay. Functional outcomes were assessed using a neurological deficit test.
Caged Z-DEVD-aminoluciferin was validated and assessed as an adequate tool for monitoring apoptosis. Longitudinal in vivo measurement of apoptosis is challenging and requires thorough validation and normalization. No total difference in apoptosis between the used strains was found. However, in the absence of the TLR2 receptor, a more pronounced mechanism of necrosis arose. In the acute period, CAG-luc-Tlr2-/- mice had better survival than CAG-luc mice. In the chronic period, there was no difference in survival between the strains. However, magnetic resonance imaging showed that CAG-luc-Tlr2-/- lost more ipsilateral hemisphere tissue than CAG-luc mice during the chronic period. Therefore, although lower levels of inflammation may be protective in the acute period post-stroke, long-term recovery is impaired
Forms and legal effects of apparent concurrence in Croatian criminal lawv
No full textPrividni stjecaj, iako nije zakonski institut, vrlo često se pojavljuje u sudskoj praksi. Riječ je o situaciji u kojoj počinitelj s jednom ili s više radnji ispunjava bića dvaju ili više kaznenih djela, ali se osuđuje samo za jedno. Teorija razlikuje četiri oblika prividnog stjecaja. Općeprihvaćeni oblici su specijalnost, supsidijarnost i konsumpcija dok se alternativitet smatra spornim. Pregledavajući dostupnu literaturu, zaključuje se kako pojam prividnog stjecaja nije detaljno razrađen i analiziran. Od sredine 20. stoljeća nisu zabilježene značajnije promjene niti se hrvatska kaznenopravna teorija upuštala u dublju analizu ovog instituta. Doktorska disertacija polazi od činjenice kako je potrebno provesti istraživanje o tome koji se oblici prividnog stjecaja javljaju u hrvatskom kaznenom pravu, u poredbenim pravnim sustavima kao i u hrvatskoj sudskoj praksi te koji su njegovi pravni učinci. Kako bi se utvrdile sličnosti i razlike, u doktorskoj disertaciji uspoređen je institut prividnog stjecaja sa zakonski uređenim institutima i to s produljenim kaznenim djelom i beznačajnim djelom. Osim toga, posebno je analiziran prividni stjecaj u odnosu na načelo ne bis in idem i na Blockburger test. Kako bi se utvrdilo koji oblici prividnog stjecaja postoje u sudskoj praksi te je li sudska praksa po pitanju prividnog stjecaj ujednačena ili postoje različita pravna stajališta, provedeno je istraživanje koje je obuhvatilo sudske odluke od 2013. do 2024. godine pred različitim općinskim i županijskim sudovima, Visokim kaznenim sudom Republike Hrvatske i Vrhovnim sudom Republike Hrvatske. Poseban naglasak stavljen je na određena kaznena djela kod kojih se prividni stjecaj najčešće pojavljuje, kao što je kazneno djelo prijetnje, kazneno djelo nasilja u obitelji i kazneno djelo tjelesne ozljede. Iz široke analize, iznijet će se sažetak zaključaka do kojih se došlo razmatranjem prividnog stjecaja u poredbenim sustavima, hrvatskoj kaznenoj literaturi i sudskoj praksi te će se ukazati na nova rješenja i smjernice po pitanju prividnog stjecaja kako bi se otklonilo neujednačeno postupanje sudova, a posljedično i nesigurnost građana u pravni poredak. S obzirom da prividni stjecaj nije zakonski institut, u radu će se osvrnuti i na mogućnost zakonskog uređenja ovog instituta.Apparent concurrence, although not a legal institute, frequently appears in judicial practice. It refers to a situation where the perpetrator, with one or more actions, fulfills the elements of two or more criminal offenses but is convicted for only one. The theory distinguishes four forms of apparent concurrence. The generally accepted forms are specialty, subsidiarity and consumption, while alternativity is considered controversial. Upon reviewing the available literature, it is concluded that the concept of apparent concurrence has not been thoroughly elaborated or analyzed. Since the mid-20th century, there have been no significant changes, nor has Croatian criminal law theory delved into a deeper analysis of this institute. This doctoral dissertation is based on the fact that research is needed on which forms of apparent concurrence appear in Croatian criminal law, in comparative legal systems, as well as in Croatian judicial practice, and what its legal effects are. In order to determine the similarities and differences, the doctoral dissertation compares the institute of apparent concurrence with legally regulated institutes, namely, with the continuing offense and the insignificant offense. Additionally, apparent concurrence is specifically analyzed in relation to the principle of ne bis in idem and the Blockburger test. To determine which forms of apparent concurrence exist in judicial practice and whether judicial practice on the issue of apparent concurrence is consistent or if there are different legal positions, research was conducted covering final court decisions from 2013. to 2024. from various municipal and county courts, the High Criminal Court of the Republic of Croatia, and the Supreme Court of the Republic of Croatia. Special emphasis is placed on certain criminal offenses where apparent concurrence most commonly occurs, such as the criminal offense of threats, the criminal offense of domestic violence, and the criminal offense of bodily injury. From the broad analysis, a summary of the conclusions reached by examining apparent concurrence in comparative systems, Croatian criminal literature, and judicial practice will be presented, and new solutions and guidelines on the issue of apparent concurrence will be suggested to eliminate inconsistent court practices, and consequently, citizens' insecurity in the legal system. Since apparent concurrence is not a legal institute, a doctoral dissertation will also consider the possibility of legally regulating this institute
Molecular diversity among adult hippocampal and entorhinal cells
No full textThe hippocampal system is a critical component in cognition, adult neurogenesis, and selectively sensitive to aging and neurodegenerative processes. To gain insights into neurogenic potential and diversity of cell types in adult humans, we profiled single-nucleus transcriptomes in five hippocampal subregions. Integration of dentate gyrus data with mouse, pig and macaque, showed strong neurogenesis trajectories in these species that was absent in humans. Doublecortin (DCX), the common marker of neurogenesis in the dentate gyrus, showed widespread expression in the human hippocampal system, including some mature
dentate granule cells, but did not define immature cell populations in humans. We further revealed prominent diversity among excitatory neurons across the hippocampal system that echoed the transition from three-layered archicortex to six-layered neocortex. Our results highlighted the uncharacterized METTL7B associated with Alzheimer’s disease-related proteins and enriched in primates in neuronal subtypes and subregions more resilient to early neuropathological changes in the Alzheimer’s disease. Overall, our findings unveiled cell typespecific molecular characteristics pertinent to hippocampal physiological function.Neuralni krugovi hipokampalne (HIP) i entorinalne moždane kore (EC) ključni su dijelovi široke neuronske mreže odgovorne za pamćenje te reprezentaciju prostora i vremena. U svrhu boljeg uvida u pojedinačne neuronske i ne-neuronske populacije tog sustava, provedeno je RNA sekvencioniranje pojedinačnih staničnih jezgara (snRNA-seq) uzoraka iz pet anatomski definiranih podregija hipokampalnog sustava. Integrirana analiza između vrsta pokazala je transkriptomske i histološke znakove neurogeneze u odraslim miševima, svinjama i makaki majmunima, ali ne i u ljudi. DCX, marker novonastalih zrnatih stanica, pronađen je u različitim neuronskim populacijama odraslog čovjeka, ali nije definirao populacije nezrelih neurona. Također, opisali smo specifične, subregionalno transkriptomski definirane tipove stanica i promjene u prijelazu iz troslojnog arhikorteksa u šestoslojni neokorteks. Naši rezultati istaknuli su da je METTL7B povezan s proteinima povezanim s Alzheimerovom bolešću i obogaćen u primata u podtipovima stanica i podregijama otpornijim na rane neuropatološke promjene u Alzheimerovoj bolesti. Ovo istraživanje je otkrilo molekularne karakteristike određenih vrsta i podtipova stanica koje potencijalno imaju važnu ulogu u fiziološkoj funkciji i/ili patološkim promjenama hipokampalnog sustava