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Supervision of Associations in Croatian and Comparative Law
No full textPravo na slobodu udruživanja jedno je od temeljnih ljudskih prava zajamčenih kako najznačajnijim međunarodnim ugovorima tako i propisima Republike Hrvatske i drugih europskih država. Upravo navedeno ljudsko pravo predstavlja osnovu za dobrovoljno udruživanje građana sa svrhom ostvarenja i ispunjavanja najrazličitijih ciljeva i zadaća. Jedan od najznačajnijih, a i najčešćih organizacijskih oblika kojim se ostvaruje pravo na slobodu udruživanja jesu udruge.
Udruge koje predstavljaju realizaciju slobode udruživanja uživaju stanovitu autonomiju. Međutim, autonomija udruga nije posvemašnja, već je ograničena provođenjem nadzora nad osnivanjem udruga, njihovim djelovanjem i prestankom njihova rada te pitanjima odgovornosti udruge i njezinih članova za utvrđene povrede kao i zaštite članova od nezakonitog postupanja udruge. Naime, nadzor nad pravnim osobama koje slijede privatne ciljeve i interese odlikuje se posebnim karakteristikama čija je osnovna svrha utvrđenje poštovanja unaprijed propisanih pravila. To je od osobitog značaja upravo za udruge koje su najbrojnije neprofitne organizacije kako bi se s jedne strane zajamčila sloboda udruživanja, a s druge strane omogućila zaštita javnog interesa kao i interesa trećih osoba od nezakonitog postupanja takvog oblika udruživanja.
Unatoč navedenom, određena zakonska rješenja u provođenju nadzora nad udrugama u hrvatskom pravu, kao i praksa hrvatskih sudova, nisu u suglasnosti s europskim propisima niti propisima promatranih europskih država. To se prvenstveno odnosi na manjkavost propisa u provođenju preventivnog nadzora, tj. nadzora koji se provodi pri osnivanju udruga. Manjkavost propisa odnosi se i na provođenje naknadnog nadzora koji se provodi nakon što je udruga započela sa svojim djelovanjem i to na propise o tijelima udruge i nadzoru nad njihovim radom, nadzornim mehanizmima zaštite članova udruge, nadzoru nad djelovanjem udruga te odgovornosti članova udruge za utvrđene povrede. Cilj ove doktorske disertacije je doprinijeti razjašnjenju otvorenih pitanja u pravnoj regulaciji nadzora nad udrugama i području njihovog djelovanja te prijedlozima unaprijediti pravni okvir udruga u Republici Hrvatskoj, na temelju sveobuhvatne analize postojeće zakonske regulative i sudske prakse u Republici Hrvatskoj te prikaza postojećih pravnih rješenja u usporednom pravu.The right to freedom of association is one of the fundamental human rights guaranteed by both, the most important international treaties and the national laws of the Republic of Croatia and other European states. This human right represents the basis for voluntary association of citizens with the purpose of achieving and fulfilling various goals and tasks. One of the most important and most common organizational forms whereby citizens exercise the right to freedom of association are associations.
As means to realize the freedom of association, associations enjoy certain autonomy. However, the autonomy of associations is far from absolute; it is limited not only by enforcing the supervision in the course of its founding, operation and dissolution, but also by ensuring that the association and its members are responsible for the violations established by the competent authorities and that the members are protected from illegal acts of the association. Generally, the supervision of legal persons that pursue private goals and interests is identified by special regulatory features whose main purpose is to establish strict compliance with the prescribed rules. This is of particular relevance to associations, the most numerous non-profit organizations, which on the one hand guarantee freedom of association, and on the other hand facilitate protection of the public interest and the interest of third parties from the illegal acts of associations.
However, certain provisions concerning the supervision over associations in Croatian law, together with Croatian case law, are not consistent with European legal instruments or laws of the analyzed European states. This primarily refers to the inadequacies in the laws which regulate the implementation of preventive supervision, i.e., supervision carried out at the founding of an association. The inadequacy further relates to the implementation of subsequent supervision, which is carried out after the association has been founded and when it has already commenced its activities, namely the rules concerning the bodies governing the association and supervision of their operation, supervisory mechanisms for the protection of members of the association, supervision over the activities of associations and responsibility of members of the association for violations established by the supervisory authorities. Therefore, the aim of this doctoral dissertation is to contribute to understanding open issues related to the legal regulation of supervision of associations and improving the legal framework for associations in the Republic of Croatia, by means of a comprehensive analysis of the current legislation and case law in the Republic of Croatia and by existing legal solutions in comparative law
The impact of formal institutions on investment structure
No full textGlavni cilj ovog doktorskog rada je istražiti utjecaj formalnih institucija na strukturu investicija 22 europske zemlje u vremenskom periodu od 2011. do 2017. godine. Pregledom literature, uočen je literaturni jaz u smislu izučavanja povezanosti između formalnih institucija i strukture investicija. Naime, u većini empirijskih istraživanja autori su davali prednost gospodarskom rastu, poduzetništvu i izravnim stranim ulaganjima, zanemarujući potencijalni učinak formalnih institucija na strukturu investicija u gospodarstvu. Polazeći od funkcije investicija kao teorijske podloge, rezultati panel analize s fiksnim i sa slučajnim efektima pokazuju da jednostavniji postupci osnivanja poduzeća djelomično utječu na strukturu investicija. S druge pak strane, zaštita vlasničkih prava i pravna provedba ugovora pokazale su se ključnim determinantama institucionalnog okvira koje značajno utječu na povećanje ukupnih investicija u građevinarstvu. Širenjem analize na investicije u stambene objekte, istraživanje je pokazalo da poboljšanje kvalitete regulacije uzeto samo za sebe nije dostatno za značajnije povećanje investicija u stambene objekte. Međutim, unaprjeđenje kvalitete regulacije, uz istodobno poboljšanje institucionalnog okvira u vidu većeg stupnja neovisnosti pravosuđa, zaštite vlasničkih prava te pravne provedbe ugovora, dovodi do dijametralno suprotnih rezultata, odnosno značajnog povećanja investicija u stambene objekte.The main goal of this doctoral thesis is to investigate the impact of formal institutions on the structure of investments, in 22 European countries in the period 2011-2017. One of the main challenges of studying the field of institutional economics is related to defining the concept of formal institutions. Namely, the literature review found that there is no consensus on the most appropriate way to define the concept of formal institutions in the economy. The reason can probably be found in the fact that one definition cannot include everything that formal institutions represent. Due to that, this doctoral thesis defines formal institutions as a legislative framework, within which entire economic activity of a certain country takes place, and can be adapted very quickly to new economic circumstances, while being under the government's authority. Furthermore, a literature gap was indentifed in terms of studying the relationship between formal institutions and the structure of investments. Namely, the majority of existing empirical research gave priority to economic growth, entrepreneurship and direct foreign investments, ignoring the potential effect of formal institutions on the structure of investments in the economy. As a result of the identified literature gap, four main hypotheses were formed in this doctoral thesis:
H1: The simplicity of starting a business affects the structure of investments,
H2: A higher degree of property rights protection significantly affects the increase of total investments in construction,
H3: A higher degree of legal enforcement of contracts significantly affects the increase of total investments in construction and
H4. The regulatory quality affects the increase of investments in dwellings.
Starting with the investment function as a theoretical basis, the results of the panel analysis with fixed and random effects resulted in partial acceptance of hypothesis H1, complete acceptance of hypotheses H2 and H3, and rejection of hypothesis H3. However, in addition to testing the aforementioned hypotheses, the doctoral thesis also includes an additional analysis related to investments in dwellings. By introducing interactive members, research has shown that improving the regulatory quality, along with the simultaneous improvement of the institutional framework in the form of a greater degree of judiciary independence, protection of property rights and legal enforcement of contracts, leads to a significant increase in dwellings investment. The results of the analysis clearly indicate that sometimes the combination of two or more policies by policymakers can produce better effects in the economy than in the case of taking only one measure
Performance based maintenance contracting model
No full textRedovito i adekvatno održavanje prometnica uz opće prisutan zaostatak u održavanju cestovne infrastrukture te sve veći zahtjevi po pitanju cestovne sigurnosti stavljaju velik izazov pred tradicionalne modele održavanja temeljene na izvedenim količinama, a kao njihova alternativa nameću se modeli održavanja prometnica temeljeni na učincima. Pregledom literature utvrđen je niz prednosti modela održavanja temeljenih na učincima, a kao jedan od većih nedostataka utvrđena je kompleksnost njihova ugovaranja proizašla iz velikog broja parametara održavanja. Ova disertacija prikazuje razvoj ugovornog modela održavanja prometnica temeljenog na učincima iz aspekta odabira parametara održavanja s ciljem jednostavnijeg i efikasnijeg ugovaranja radova održavanja prometnica uz istovremeno postizanje ključnih prednosti održavanja temeljenog na učincima odnosno smanjenja troškova održavanja te povećanja sigurnosti prometa i kvalitete izvedenih radova. Ugovornim modelom sve navedeno se postiže na način da se kod njegova formiranja odabire minimalan broj samo onih parametara održavanja koji su istovremeno ostvarivi, u skladu sa ciljevima svih interesnih sudionika te doprinose ostvarenju ključnih prednosti održavanja temeljenog na učincima. Osnovna pretpostavka navedenog modela leži u činjenici kako svaki parametar jednako doprinosi složenosti procesa ugovaranja i provedbe ugovora, a da svaki parametar istovremeno ne doprinosi jednako ostvarenju zadanih ciljeva niti ostvarenju ključnih prednosti održavanja prometnica temeljenog na učincima. Nakon pregleda i analize dostupne literature navedeni su svi bitni elementi i rizici procesa odabira parametara održavanja kao i važnost njihove usklađenosti sa zakonskom regulativom, krajnjim ciljevima i cestovnom politikom. Potom je formiran stručni tim koji je definirao način i vrednovanje odabira ukupnog broja ponuđenih parametara održavanja te iste odabrao i rasporedio unutar svake skupine parametara ugovornog modela. Nakon toga izvršena je validacija predmetnog ugovornog modela kroz dvije faze, putem anketnog upitnika i putem intervjua. Anketni upitnik je proveden pomoću programa LimeSurvey među 71 ispitanikom čiji odgovori su zajedno analizirani u programu IBM SPSS v.27 dok je intervju proveden sa 3 ispitanika koji su zaposleni u samom vrhu nekoliko sustava upravljanja i odlučivanja o cestovnom prometnom sektoru u Republici Hrvatskoj. Provedenim istraživanjem potvrđena je hipoteza istraživanja te je dokazano kako se primjenom predmetnog modela održavanja temeljenog na učincima može povećati efikasnost i učinkovitost održavanja prometnica te sigurnost prometa.1. Introduction
This dissertation presents the development of a performance-based road maintenance contract model (model). The aforementioned contract model was developed with the aim of reducing the complexity of the performance-based road maintenance contracting process, while at the same time realizing the key advantages that performance-based road maintenance brings, (increasing the quality of performed works, reducing long-term maintenance costs and increasing traffic safety). Also, the developed model can contribute to the reduction of the backlog in the maintenance of road transport infrastructure, which was observed by reviewing the existing literature. All of the above is achieved by the contract model of performance-based road maintenance by combining the broad and rich knowledge of adequate experts in the field of road management and maintenance and by focusing on key performance indicators. The basic assumption of the mentioned model is that each selected performance indicator of a performance-based road maintenance contract further increases the complexity of the process of its creation and contracting, as well as its subsequent implementation, but at the same time each selected performance indicator doesn’t affect the achievement of the key benefits of performance-based road maintenance. A review of the literature revealed that many studies focus on the implementation phase of road maintenance with the application of performance-based contracts and their results, while a smaller number of them focus on the contract creation phase and the contracting process itself. Furthermore, a large number of conducted researches generally deal with the elements that must be covered and included during the creation of a new performance-based road maintenance contract, and a small number of them focus on the selection of performance indicators itself. In conclusion, research dealing with performance indicators and their selection as part of the contracting process is in the vast majority of cases focused on the selection of characteristics of performance indicators and their associated levels, which need to be achieved during contract implementation. Therefore, this research contributes to the area of performance-based road maintenance by developing a conceptually universal contract model from the aspect of selecting the performance indicators themselves and their adequate number. The developed model can be applied for performance-based contracting of road maintenance works for regular maintenance of roads and highways, but also for comprehensive maintenance of the mentioned and all other categories of roads, with certain modifications and adjustments and its upgrading.
2. Elaboration of the current condition of the road maintenance in Europe and the Republic of Croatia
2.1. Analysis of the current condition of the road maintenance in European countries
By reviewing the literature and all available current data, a tabular presentation of all data for individual countries of the European Union and the rest of Europe on road safety in terms of the number of injured and killed in traffic and the trend of their movement is given. Then, data on the individual and total length of all roads and their traffic load, the type and amounts of financial investments, the production and use of asphalt and asphalt mixtures and the companies that deal with it, as well as data on the computerization of roads and their monitoring and management systems, are presented. Finally, the overall evaluations of the quality of the road transport infrastructure of each country are presented.
2.2. Conclusion of the analysis of the current situation of road maintenance in European countries
From all the collected data, as well as the related reviewed literature, a conclusion about the current condition of the road maintenance in the European Union and the rest of Europe was given, from which it is evident that road safety isn’t at a satisfactory level and that the goals set by the European Union until 2020. years related to security fulfilled only by a small number of countries. Also, the trend of investment in the maintenance of road transport infrastructure is variable on average, which means that there is a rise and fall in investment in maintenance, which implies negative consequences for the quality of road transport infrastructure, as well as safety. Also, irregular and inadequate investments in maintenance lead to the appearance of a backlog in the maintenance of road transport infrastructure, or its additional increase in countries where it is already present, with all the negative consequences it brings. As a logical answer to everything shown, performance-based road maintenance, which was presented in the first chapter of this paper, is presented, with all the advantages it brings. All of the above is sufficient motivation for the creation of a contract model of performance-based road maintenance, which will be able to ensure an increase in the quality of the performed works, a reduction of long-term road maintenance costs and an increase in the level of road traffic safety (which is the most important thing) in all conditions.
3. Performance-based road maintenance
3.1. Road maintenance
The review of the available literature shows the definitions of the basic terms related to roads, their systematization and the defined division of road maintenance in the world and in the Republic of Croatia. Also, the importance and impact of regular and adequate road maintenance on the economy, safety and traffic costs, the value of road assets, and the mutual relationship and impact of roads on the environment, as well as the impact and relationship of the environment and climate change on road maintenance, are presented.
3.2. Backlog in road maintenance
The backlog in road maintenance is a consequence of irregular and inadequate maintenance of roads and other road assets, most often resulting from an insufficient amount of financial resources for maintenance. In the long term, the aforementioned backlog in road maintenance has significantly negative consequences for the safety of roads, as well as the value of their property. With regard to the available data, the condition of the backlog in road maintenance at the world and European level is described, with exact financial amounts for some European countries, and the general reasons for its occurrence in Europe are stated, as well as the influence of performance-based road maintenance models on its reduction.
3.3. Performance-based road maintenance
Performance-based road maintenance, in comparison to traditional maintenance based on performed quantities, bases the success and performance of activities on the achieved predefined maintenance parameters. The history of its creation is described and all areas of its application are listed, as well as the basic reasons for its introduction in the field of construction and maintenance of road transport infrastructure. All its advantages and disadvantages are analysed and described, and all necessary assumptions for its successful implementation are described in detail.
4. Performance-based road maintenance contract model
4.1. All-important prerequisites of the maintenance parameter selection process
Performance-based road maintenance contract model was developed as part of this research, with the aim of enabling the simplest possible way of selecting adequate maintenance parameters, while considering all essential elements, accompanying risks and all participants in the process of selecting maintenance parameters, as well as the compliance of the selected parameters with the legal framework and road policy. In the research, all the essential prerequisites and elements of the model parameter selection process are listed, and the most important fact is that the development of maintenance parameters must be part of the early phase of contract development and implementation, and their selection should be based on current data on the condition of the road. Also, it is important to emphasize that the parameters and their default goals must not overlap, or in an even worse case, exclude each other. Therefore, when selecting them, it is necessary to answer the questions whether each selected maintenance parameter is:
• Specific
• Achievable
• Results-oriented
• Measurable
• Timely
• In accordance with the policy of the agency that manages the road
• Whether the parameter has already been used earlier on that road?
• Is it in line with the interests of all participants?
• Is it in line with previous maintenance results, or does it require a higher level of
execution and achieved quality than before?
• Will the parameter and its required level raise the overall maintenance score?
• Is the parameter available considering the available financial resources?
Each selected parameter must reflect the set goals, enable their achievement, and must be simple and unambiguous, so that its realization, monitoring and control are as simple as possible, and so that the selected parameters have as little influence on the complexity of contract drafting and implementation. The key emphasis when selecting the maintenance parameters must be on the professional knowledge and long-term experience of the persons (experts) participating in the process, which was achieved during the creation of the model as part of this research, in order to avoid possible risks. Possible risks related with the process of selecting maintenance parameters arise from two directions. The first group of risks arises from the maintenance parameters themselves or is directly related to them, while the second group of risks is indirectly related to the maintenance parameters. The causes of both groups of risks primarily lie in two key elements and their lack will certainly activate some of the risks from the two mentioned groups. These are professional staff who have adequate knowledge and experience in selecting valid maintenance parameters for a certain specific performance-based road maintenance contract, who will be able to see everything necessary for their proper selection with their knowledge and experience, and the second is adequate and accurate data on the current condition of the roads. It should be pointed out that the lack of the first essential element, professional and adequate staff, can be replaced by hiring external experts (consultants), who have the necessary knowledge and experience, while the second element, adequate and accurate data, can only be replaced by expertise of the current condition of the road, which will to collect all the necessary and relevant data about the road, which are necessary for the proper selection of maintenance parameters. By providing these two key elements (professional staff and adequate and accurate data), all possible risks related to the process of selecting maintenance parameters can be significantly reduced (minimized). All the mentioned risks from both groups of risks are listed in this research, and guidelines for their complete elimination are given, or the maximum possible mitigation of the impact on the parameter selection process and its final result. Also, as part of the research, the importance and role of all stakeholders in the parameter selection process was elaborated. Stakeholders in the selection of maintenance parameters are all those who have a certain interest in the maintenance, and that is why during the mentioned process care must be taken to ensure that the selection of the required parameters comprehensively satisfies all the necessary functional, technical, ecological, safety, economic and institutional considerations and needs are comprehensively satisfied by the selection of the required parameters, as well as set goals. All stakeholders can be divided into two groups, direct and indirect, among which the most important is the direct group of stakeholders. Direct stakeholders are:
• road management agency and consultants,
• potential contractors,
• users of the road.
The aforementioned group of stakeholders is the most important, and the road management agency stands out among them, since it is the stakeholder that makes all the final decisions, considering the interests of all other stakeholders of both groups. All other participants belong to the indirect group of stakeholders, who in some way have an interest in the maintenance process and whose goals, to a greater or lesser extent, need to be met, and whose fulfilment is again the responsibility of the road management agency. Indirect stakeholders are:
• the Ministry of Finance and the Ministry of Transport and Infrastructure,
• associations for environmental protection,
• government representatives and road policy makers,
• tourist Board,
• health representatives and representatives of rural development,
• associations of drivers and road carriers,
• other business and non-governmental organizations.
Potential contractors, members of the first group of stakeholders, are very important it this process, because they are the balance between possible wishes and set maintenance goals and the possibilities that potential contractors can present with regard to the given financial frameworks. Potential contractors have a dual role in the process of selecting maintenance parameters. Their primary role is to participate in the parameter selection process to get to know all the requirements and wishes that the road management agency will put before them by selecting the parameters, and to clarify all possible ambiguities in their interpretation, and their second role is to present all their options with regard to capacities and the experience they have, with the intention that the agency defines the parameters and set goals that the contractors can achieve. According to the above, in the process of selecting maintenance parameters, the most important role is played by the road management agency, together with its consultants, which ultimately selects all maintenance parameters and states them in the contract, considering all previously mentioned selection elements, as well as the goals of all stakeholders and their priorities.
Also, during the process of selecting maintenance parameters, one more important element should be considered: compliance of the selected parameters with the laws and valid technical and other regulations of the country where the contract is formed. Therefore, when choosing the parameters, it is necessary to study the legal regulations, technical standards and other acts where the minimum criteria for certain categories of roads are stated, and it is necessary to harmonize the parameters with this, at the same time taking care that the selection of individual maintenance parameters doesn’t duplicate certain conditions and requirements for road maintenance, which have already been previously defined by the mentioned legal and technical framework and which can be simply put in the general conditions of the maintenance contract. This will avoid the negative effect of a large number of unnecessary maintenance parameters on increasing the complexity of the contracting process and its subsequent implementation, and at the same time will condition the execution of all activities in accordance with the entire applicable legal framework and technical regulations. In the end, the process of selecting maintenance parameters, in addition to the aforementioned compliance with the applicable legal framework and all technical regulations, must also be aligned with the goals of the national road policy. There are several reasons for this, and among the most important are the fact that states implement the main goals of road transport systems at the highest level with their road policies, which means that they meet the needs and goals (such as that of the European Commission on reducing the number of road traffic fatalities by 50% until 2030), or they want to achieve certain savings in road management and maintenance costs at the level of all road systems in their territory.
When the relevant ministries define all the goals that they want to achieve by introducing performance-based road maintenance, it is important to determine and define all maintenance parameters so that they meet the previously set goals, so that the road management agencies receive all the support for the implementation and development of road maintenance using this model. as well as the necessary financial resources for their realization. During the selection of parameters, it is necessary to take care that the selected goals aren’t unnecessarily set too high in relation to expectations, since these can affect the increase in the complexity of the contracts and even more the increase in the total costs of their implementation. The only aspect in which the given goals must not have the restrictions is road safety. And finally, it is necessary that the road management agency, during the selection of maintenance parameters, takes care of the mutual alignment of all its goals with the goals of the state road policy, which means that the goals are not mutually exclusive.
4.2. Establishing an expert team for the process of selecting maintenance parameters
Given the fact that the process of selecting maintenance parameters for the contract model of performance-based road maintenance is a fundamental and key step in the formation of the specified type of road maintenance contract, and on which its success largely depends, it needs to be approached with the utmost care and is important for its implementation provide all the necessary elements, and the most important element is the knowledge and experience of experts who select the specified parameters and form a contract model (a maintenance contract). For the purposes of this research, an expert team was formed, which consisted of 7 experts in the field of road management and maintenance, and they had to meet specific conditions. Also, the procedure for selecting the total number of necessary maintenance parameters, as well as the
number of their groups, is described, based on all the analysed data of similar existing performance-based road maintenance contracts, as well as the existing guidelines for contracting the relevant contracts issued by the World Bank, considering all the previously mentioned essential elements of the process of selecting maintenance parameters. The aforementioned team was formed with the aim of expertly selecting groups of parameters, maintenance parameters belonging to them and their total number, in accordance with the latest scientific achievements and research, the latest available examples of contracts and guidelines for contracting performance-based road maintenance contracts, the current legal framework of the Republic of Croatia, as well as all technical conditions and regulations related to the road management and maintenance.
4.3. The process and result of the maintenance parameter selection process
Once the most important condition for starting the process of selecting maintenance parameters has been implemented and the expert
Kratki linearni i ciklicki katalitički peptidi inspirirani esterazom
No full textIn this dissertation, two key approaches for the design of catalytic peptides are explored: (i) the incorporation of amino acids from the catalytic triad and (ii) an approach
involving metal ions. To identify these main design approaches, a comprehensive dataset
based on the collection of published data about purely peptidic catalysts for ester hydrolysis was gathered and analyzed including both active and inactive sequences tested
towards the p-NPA and p-NPP substrates providing an insight into the currently developed
catalytic mechanisms. Additionally, this open-access dataset also includes the SMILESbased representation of peptides and it can be used for training of machine learning-based
models. Moreover, the standard p-NPA method was optimized. This extensively employed assay for determining catalytic activity, initially designed for enzymatic reactions,
is not directly applicable to peptides due to variations in reaction parameters, such as
the concentrations of catalysts and reaction times, when comparing peptides to enzymes.
Consequently, standardizing conditions, including temperature, pH, buffer choice, and
concentrations of both substrate and peptide, became essential to ensure accurate and
reliable results in peptide reactions. Furthermore, the synthesis of a set of histidine-rich
linear and cyclic peptides allowed us to understand the impact of amino acid arrangement,
cyclization, and inclusion of D-amino acids on their self-assembly, coordination of Zn2+
ions and ability to hydrolyze p-NPA. Investigating structural changes crucial to the functionality of short peptides contributes to the development of a new generation of catalytic
peptides and advances our understanding of the potential of self-assembly in improving
catalytic efficiency. Additionally, we investigated the feasibility of isolating the active
site of an enzyme to develop a minimalist catalyst, with a specific focus on recognizing
cysteine as a crucial component within the catalytic triad, essential for the effectiveness
of the peptide catalyst. The synthesis of a set of cysteine-rich peptides showing tunable
activity resulting from the sensitivity of the thiol groups to the redox environment could
open promising opportunities for tailored enzymatic catalysis. The overall goal of this
research is to gain a deeper insight into the relationship between the sequence and function of catalytic peptides, leading to the development of innovative peptide catalysts with
potential applications in various fields, including biocatalysis, pharmaceutical synthesis,
and other industrial processes.U ovoj disertaciji predstavljena su dva kljucna pristupa za dizajn katalitičkih peptida: (i) peptidne sekvence bazirane na aminokiselinama iz kataliticke trijade i (ii) pristup koji se temelji na interakciji peptida i metalnih iona. U svrhu identifikacije ovih glavnih pristupa, prikupljen je i analiziran sveobuhvatan skup podataka na temelju objavljenih katalitičkih peptida za hidrolizu estera, uključujući aktivne i neaktivne sekvence testirane na supstratima p-NPA i p-NPP, pružajuci uvid u trenutno razvijene katalitičke mehanizme. Ovaj skup podataka s otvorenim pristupom ukljucuje i računalnu reprezentaciju peptida u formatu SMILES koja se može koristiti za treniranje i razvoj modela zasnovanih na strojnom ucenju. Nadalje, optimizirana je standardna metoda p-NPA za određivanje katalitičke aktivnosti. Ovaj često korišteni esej, prvotno dizajniran za enzime, nije
izravno primjenjiv na peptide zbog varijacija u parametrima katalitiče reakcije, kao što su koncentracija katalizatora i trajanje reakcije u usporedbi peptida s enzimima. Stoga je bilo potrebno standardizirati uvjete, uključujući temperaturu, pH, izbor pufera i koncentracije supstrata i peptida, kako bi se osigurali tocni i pouzdani rezultati. Nadalje, sinteza skupa linearnih i ciklickih peptida bogatih histidinima omogućila nam je razumijevanje utjecaja rasporeda aminokiselina, ciklizacije i uključivanja D-aminokiselina na njihovu sposobnost samo-sastavljanja, koordinacije iona Zn2+ i sposobnost hidrolize pNPA. Istraživanje strukturnih promjena kljucnih za funkcionalnost kratkih peptida doprinosi razvoju nove generacije katalitičkih peptida i unaprjeđuje naše razumijevanje potencijala samo-sastavljanja u poboljšanju katalitičke učinkovitosti. Dodatno, ispitana je mogućnost izdvajanja aktivnog mjesta enzima radi razvoja minimalističkog katalitičkog peptida, s posebnim naglaskom na cistein kao ključnoj komponenti unutar katalitičke trijade, neophodnoj za učinkovitost takvih peptida. Sinteza seta cisteinom bogatih peptida koji pokazuju prilagodljivu aktivnost kao rezultat osjetljivosti tiolnih skupina na redoks okolinu, otvara nove mogućnosti za prilagodljivu peptidom posredovanu katalizu. Glavni cilj ovog istraživanja je razumjeti odnos izmedu sekvence i funkcije katalitičkih peptida, čime bi se omogućio razvoj inovativnih katalitičkih peptida primjenjivih u različitim područjima, uključujući biokatalizu, sintezu lijekova i industrijske procese
Perception of authenticity and value of digital content as a prerequisite of consumer engagement with branded digital content in the fashion industry
No full textOvaj doktorski rad istražuje dinamiku između potrošača i digitalnog sadržaja marke u industriji mode, fokusirajući se prvenstveno na potrošačev angažman s digitalnim sadržajem marke. Temeljem opsežne analize literature iz područja potrošačevog angažmana i digitalnog marketinga, uz integraciju ključnih postojećih teorijskih okvira, oblikovan je novi teorijski okvir prilagođen specifičnim potrebama ovog istraživanja. Ovaj okvir kritične varijable suvremenog marketinga postavlja u potpuno novi kontekst - kontekst digitalnog sadržaja. Istraživanje razotkriva kako percipirana autentičnost digitalnog sadržaja marke, te njegova hedonistička i utilitarna vrijednost, utječu na različite aspekte potrošačevog angažmana. Analizom je utvrđeno da percipirana autentičnost digitalnog sadržaja igra ključnu ulogu u pojačavanju intenziteta potrošačevog angažmana, obuhvaćajući dimenzije konzumacije, reakcije i kreacije digitalnog sadržaja. Dalje, istraživanje otkriva da utilitarna i hedonistička vrijednost digitalnog sadržaja imaju različit utjecaj na različite dimenzije potrošačevog angažmana, što ukazuje na složenost i multidimenzionalnost potrošačevih ponašanja u digitalnom okruženju, ali i na kompleksnost, odnosno neovisnost, različitih dimenzija potrošačeva angažmana s digitalnim sadržajem marke. Ovo istraživanje otvara sasvim novu potrebu za dodatnim istraživanjima o višeslojnosti i konzistentnosti ponašanja potrošača, s posebnim naglaskom na različite manifestacije sklonosti samopovezivanju s markom i namjere upotrebe marke između između digitalnog i fizičkog svijeta, kao i između različitih generacija. Doktorski rad pruža novi uvid u kompleksnu interakciju između potrošača i digitalnog sadržaja marke te nudi nove perspektive za razumijevanje potrošačkih motivacija i percepcija u kontekstu razvoja digitalnih marketinških strategija u industriji mode. Sve u svemu, rezultati ovog rada predstavljaju vrijedan doprinos teorijskim i praktičnim aspektima digitalnog marketinga, posebno u kontekstu modnog sektora.This doctoral thesis explores the dynamic between consumers and brand's digital content in the fashion industry, focusing primarily on consumer's engagement with branded digital content. Based on an extensive analysis of the literature in the fields of consumer engagement and digital marketing, coupled with the integration of key existing theoretical frameworks, a new theoretical framework has been developed, tailored specifically for the needs of this research. This framework places critical variables of contemporary marketing in an entirely new context – the context of digital content marketing. The research reveals how the perceived authenticity of a brand's digital content, along with its hedonistic and utilitarian value, influences various aspects of consumer engagement with branded digital content. The analysis has determined that the perceived authenticity of digital content plays a crucial role in enhancing the intensity of consumer engagement, encompassing dimensions of content consumption, reaction, and creation. Furthermore, the study reveals that the perceived utilitarian and hedonistic values of branded digital content differently impact various dimensions of consumer engagement, indicating the complexity and multidimensionality of consumer behavior in the digital environment of fashion, as well as the independence of different dimensions of consumer engagement with digital brand content. This research opens a new need for additional studies on the complexity and consistency of consumer behavior, with a special emphasis on different manifestations of the tendency for self-connection with the brand and the intention to use the brand between the digital and physical realms, as well as among different generations. Overall, the doctoral thesis provides new insights into the complex interaction between consumers and digital brand content and offers new perspectives for understanding consumer motivations and perceptions in the context of developing digital marketing strategies in the fashion industry. This research confirms the multilayered nature of the digital environment and the distinct complexity of content marketing. The perceived authenticity of digital content has been confirmed as a fundamental prerequisite for consumer engagement, while the remaining conclusions encourage brands to study their consumers more thoroughly in order to gain a clearer understanding of their specific motivations and desires. As stated earlier, the scientific contribution of this paper lies in the development and empirical testing of a new theoretical framework that integrates key frameworks and insights from the existing scholarly literature. All in all, this study represents the first comprehensive investigation that directly examines consumer engagement with brand digital content, focusing on critical aspects such as the perceived authenticity of the brand's digital content and the perceived hedonic and utilitarian value of the brand's digital content. These constructs are positioned in the context of digital content, rather than the brand itself, for the first time, adding an extra layer of importance to a brand's perceived behavior in the digital realm, as well as the consumer's perception of it
The influence of rhizobacterium Azospirillum brasilense on cherry rootstock and cv. Lapins vegetative growth and leaf mineral composition
No full textTrešnja (Prunus avium L.) značajna je voćna vrsta za potrošnju u svježem stanju. Najviše se uzgaja u područjima umjerenog klimata, te zbog ranijeg dozrijevanja i tehnologija uzgoja postiže relativno visoke cijene na tržištu. U intenzivnom uzgoju trešnje nove tehnologije usmjerene su na povećanje uroda i kvalitete plodova uz očuvanje zdravstvenog stanja stabala, čemu pridonosi i odabir podloga optimalne bujnosti. Sainte Lucie (SL) 64, MaxMa 14 i Gisela 5 jesu podloge manje bujnosti od sjemenjaka trešnje (P. avium), kompatibilne s velikim brojem sorti trešanja koje pokazuju dobra svojstva na različitim tipovima tla. Navedene su podloge kompatibilne sa sortom trešnje Lapins, koja je intenzivno proučavana sorta zbog svojih povoljnih svojstava kao što su sposobnost samooplodnje, rani ulazak u rod, te visoka i redovita rodnost. Rizobakterije koje potiču rast biljaka (engl. Plant Growth-Promoting Rhizobacteria) izravno ili neizravno utječu na razvoj biljke domaćina fiksacijom dušika, topljivošću teže dostupnih spojeva fosfata, sintezom fitohormona i sekundarnih metabolita, čime se povećava otpornost biljke domaćina na stresne čimbenike okoliša i prisutnost fitopatogenih mikroorganizama. Rizobakterija Azospirillum brasilense pripada skupini korisnih mikroorganizama koja asocijativno nastanjuje zonu korijenova sustava biljke domaćina, pozitivno pridonosi rastu i razvoju biljke. Današnju proizvodnju prati niz izazova s kojima se poljoprivrednici suočavaju. U voćarsku proizvodnu praksu uvode se nova rješenja s ciljem smanjenog korištenja konvencionalnih metoda gnojidbe i zaštite. Utjecaj A. brasilense na Prunus vrste do danas je nedovoljno istražen. Ciljevi ovog rada bili su utvrditi količinu mineralnih tvari u supstratu i lišću podloga SL 64, MaxMa 14 i Gisela 5, te sorte Lapins zbog primjene A. brasilense, te utvrditi vegetativnu aktivnost podloga i sorte Lapins zbog primjene A. brasilense. Poljski pokus proveden je 2022. godine na lokalitetu Poljana (otok Ugljan) na komercijalno uzgojenim jednogodišnjim sadnicama triju podloga i okulantima sorte Lapins u kontejnerima volumena 12 litara koji su bili raspoređeni po slučajnome bloknom rasporedu s trima ponavljanjima i 15 sadnica po ponavljanju za svaku podlogu. Mikrobiološki inokulat AZOS® koji sadrži rizobakteriju A. brasilense u koncentraciji od 106 CFU g-1 dodavan je 0,8 g L-1 jedanput mjesečno (T1) i 0,8 g L-1 svaki drugi mjesec (T2) u ujednačenim vremenskim intervalima, dok su istovremeno biljke u kontroli (T0) zalijevane kišnicom. Kao čimbenici vegetativne aktivnosti u obzir su uzeti visina biljke, površina poprečnog presjeka debla sadnice (engl. TCSA) i indeks sadržaja klorofila listova (engl. CCI). Osim toga, tijekom vegetacije u četiri roka bilježeni su vegetativni rast mladica, broj njihovih internodija i prosječna duljina internodija. Uzorci su listova krajem srpnja prikupljeni sa središnjeg dijela mladice i analizirani, a uzorci supstrata prikupljeni su u rujnu. Za određivanje fizikalno-kemijskih svojstava supstrata i mineralnog sastava listova korištene su sljedeće metode: u supstratu su određene vrijednosti pH, EC i % soli, a u listu suha tvar. Količina dušika određena je metodom po Kjeldahlu, a nakon digestije s HNO3 i HClO4 količina fosfora određena je spektrofotometrijski, kalija plamenfotometrijski, a kalcija i magnezija s pomoću atomskoga apsorpcijskog spektrometra. Rezultati su obrađeni dvofaktorskom analizom varijance te je proveden Tukeyjev post hoc test. Na temelju dobivenih rezultata istraživanja može se zaključiti kako je zalijevanje podloga inokulatom utjecalo na indeks sadržaja klorofila, te duljinu mladice i duljinu internodija u prvom mjerenju. Nadalje, u okulantima sorte Lapins zabilježen je utjecaj bakterije na CCI, prosječnu duljinu internodija, sadržaj amonijaka, mineralnog dušika i kalcija u supstratu, te sadržaj dušika i magnezija u listovima. U istraživanju je uočen i utjecaj podloge na mjerene vegetativne karakteristike, svojstva supstrata te mineralni sastav listova u sadnicama podloga i okulanata. Rezultati ovog istraživanja pokazuju da je inokulacija A. brasilense polučila efekt na vrijednosti sadržaja klorofila i dušika u listovima, te da se rizobakterija preporučuje rabiti kao nadopuna anorganskim ili organskim gnojivima u dobivanju kvalitetnoga sadnog materijala. Očekivani znanstveni doprinos očituje se u novim spoznajama o efektima inokulacije A. brasilense na vegetativnu aktivnost višegodišnjih vrsta iz roda Prunus, te o njezinu utjecaju na količinu mineralnih tvari u inokuliranom supstratu i biljkama.Sweet cherry (Prunus avium L.) is a valuable fruit crop for fresh consumption. It is mostly grown in areas with a moderate climate, and due to earlier ripening and cultivation technologies it achieves relatively high prices on the market. In intensive cherry production, new technologies are focusing on increasing fruit yield and quality while preserving the tree health which is also helped by the selection of rootstocks with optimal vigour. Rootstocks that are less vigorous than cherry seedlings, compatible with a large number of sweet cherry varieties and show good properties on different soil types are Sainte Lucie (SL) 64, MaxMa 14 and Gisela 5. These rootstocks are compatible with Lapins, self-fertile, highly productive and precocious fruiting cultivar. Plant growth-promoting rhizobacteria directly or indirectly affect the development of the plant by fixing nitrogen, solubilizing phosphates, synthesizing plant hormones and secondary metabolites, which increases plant resistance to environmental stress factors and the presence of phytopathogenic microorganisms. Rhizobacterium Azospirillum brasilense belongs to the group of beneficial microorganisms and associatively inhabits the plant rhizosphere. With its abilities positively contributes to the growth and development of the host plant. Nowadays, production is accompanied by a series of challenges that farmers face. New solutions are introduced in fruit production practices with the aim of reducing the use of conventional fertilization and plant protection methods. The influence of A. brasilense on Prunus spp. has been insufficiently investigated to date. Goals of this research were to determine the amount of macro elements in the substrate and leaves of three rootstocks and cv. Lapins due to the application of A. brasilense, and to determine the vegetative activity of the rootstocks and cv. Lapins due to the application of A. brasilense. The field experiment was carried out in 2022 in Poljana (the island of Ugljan) on commercially grown one-year-old maiden trees of three rootstocks and maidens of cv. Lapins in 12-liter containers that were arranged in a randomized block design with 3 replicates and 15 plants per replicate for each rootstock. Microbial inoculum AZOS® containing A. brasilense in a concentration of 106 CFU g-1 was added by watering the plants in the amount of 0 g L-1 (control plants - T0), 0.8 g L-1 once a month (T1) and 0.8 g L-1 every other month (T2) at regular time intervals. Plant height, trunk cross-sectional area and leaf chlorophyll content index (CCI) were taken into account as factors of vegetative activity. In addition, shoot growth of maiden trees, number of their internodes and the average length of internodes were noted four times during the growing season. Leaf samples were collected in the end of July from the central part of the shoot and analysed in the laboratory while substrate samples were collected in September. pH, EC and % of salt were determined in substrate, and dry matter content in leaves. Moreover, following methods were used to determine chemical properties of substrate and leaf mineral composition: mineral nitrogen content was determined by the Kjeldahl method, and after digestion with HNO3 and HClO4, the amount of phosphorus as P2O5 was determined spectrophotometrically, potassium as K2O by flame photometry, and calcium and magnesium with an atomic absorption spectrometer. Based on the obtained research results, it can be concluded that watering the plants with the inoculum affected CCI, as well as shoot length and internode length in the first measurement. Furthermore, in cv. Lapins the effect of bacteria was recorded on CCI, average length of internodes, content of ammonia, mineral nitrogen and calcium in the substrate, and nitrogen and magnesium content in the leaves. In this research, rootstock influenced the measured vegetative characteristics, substrate properties and leaf mineral composition in rootstocks and cv. Lapins maidens. Results of this research show that inoculation of A. brasilense had an effect on leaf chlorophyll values and nitrogen content and that A. brasilense can be used as a supplement to inorganic or organic fertilizers in obtaining quality planting material. Expected scientific contribution is manifested in new knowledge about the effects of A. brasilense inoculation on the vegetative activity of perennial species from the Prunus spp. and the influence of inoculation on mineral composition in plants
Model of hybrid electric vehicle in the frequency domain for consumption and emissions prediction
No full textDoktorski rad predstavlja objedinjeno istraživanje koje čine četiri objavljena rada u uglednim znanstvenim časopisima prema skandinavskom modelu. Područje znanstvenog istraživanja usmjereno je na procjene emisija i potrošnje goriva u stvarnim uvjetima upotrebe vozila primarno pokretanih motorima s unutarnjim izgaranjem. U svrhu kvalitetnijeg predviđanja emisija, potrošnje goriva i potrošnje energije razvijen je model hibridnog električnog vozila na temelju modalne analize uz primjenu odgovarajućeg dijagrama toka energije definiranog prema funkcionalnoj podjeli. Razvijeni model povezuje pojedinačne emisije i potrošnju energije s uzdužnom dinamikom vozila. Provedenim istraživanjem utvrđeno je kako je na razvijeni model moguće uspješno primijeniti globalnu strategiju upravljanja, temeljenu na pravilima, u više različitih standardnih ciklusa vožnje i u stvarnim uvjetima upotrebe. Predloženi model validiran je u odnosu na kontrolni model prema Novom europskom ciklusu ispitivanja, Globalno usklađenom ispitnom ciklusa te u okolnostima koje repliciraju stvarne uvjete upotrebe. Rezultati provedene usporedbe pokazuju točnije predviđanje emisija i potrošnje goriva sa značajno manjom relativnom pogreškom na razini ciklusa u odnosu na rezultate postojećih modalnih modela. U radu je provedeno i eksperimentalno istraživanje u cilju utvrđivanja količina emisija ispušnih plinova u stvarnim uvjetima upotrebe ispravnih vozila, kao i u slučaju vozila s kvarom na sustavima kontrole emisija. Zaključci istraživanja pridonijeli su razumijevanju utjecaja stvarnih uvjeta upotrebe kao i dugotrajne eksploatacije na emisije te sustave njihove kontrole.This doctoral thesis presents a comprehensive study comprising four published papers in reputable scientific journals, adhering to the Scandinavian model. The research primarily focuses on assessing emissions and fuel consumption under real-world conditions for vehicles primarily powered by internal combustion engines. To improve the accuracy of emission and consumption predictions, an innovative hybrid electric vehicle model was developed based on modal emissions analysis. This model incorporates energy flow diagrams that are based on their purpose. The developed model integrates the longitudinal dynamics of the vehicle and energy flows with fuel consumption and individual emissions. The research demonstrates the successful application of a global rule-based energy management strategy to the developed model across various standard driving cycles and under real-world conditions as defined by Real Driving Emissions (RDE) regulations. The model was validated against control models using the New European Driving Cycle (NEDC), Worldwide Harmonized Light Vehicles Test Cycle (WLTC), and real-world driving conditions. Comparative results show that the proposed model provides more accurate predictions of emissions and consumption, with significantly lower relative error in tested driving cycles compared to existing modal models based on Vehicle Specific Power (VSP) analysis. Additionally, the thesis includes experimental research on exhaust gas emissions from vehicles under real driving conditions. This research was conducted on both fully operational vehicles and those with malfunctioning emission control systems. The findings contribute to a deeper understanding of the impact of real-world driving conditions and long-term vehicle operation on emissions and the performance of emission control systems
Randomized clinical study of the effects of photodynamic therapy and bioceramic filling of root canals on the healing of periapical lesions and the occurence of postoperative pain after endodontic treatment
No full textSvrha doktorskog rada bila je ispitati utjecaj fotodinamske terapije i biokeramičkoga punila korijenskih kanala na cijeljenje periapikalne lezije i pojavnost postoperativnih bolova nakon jednoposjetne revizije endodontskog liječenja. Pacijenti su metodom slučajnog odabira razvrstani u dvije skupine ovisno o završnom protokolu dezinfekcije korijenskih kanala: Skupina 1. UAI (ultrazvučno aktivirano ispiranje) + Fotodinamska terapija (engl. photodynamic therapy, PDT); Skupina 2. UAI (ultrazvučno aktivirano ispiranje). Ukupno je sudjelovalo 77 pacijenata, 38 u PDT skupini i 39 u UAI skupini. U svakoj skupini, kod polovice
ispitanika, korijenski kanali punjeni su biokeramičkim punilom (BioRoot RCS, Septodont, Francuska) (Podskupina A); a druga polovica punilom temeljenim na epoksi smoli AH Plus (AH Plus, Dentsply Sirona, Sjedinjene Američke Države) (Podskupina B). Kod svih pacijenata analizirana je pojavnost i intenzitet bolova s VAS skalom boli, po danima, 7 dana nakon završetka endodontskog liječenja zuba. Kod svih pacijenata napravljena je ciljana snimka zuba konusnom kompjuteriziranom tomografijom (eng. CBCT) prije i godinu nakon revizije endodontskog liječenja. Volumen inicijalne periapikalne lezije i lezije nakon 12 mjeseci
izračunat je softverom OnDemand3D. Dobiveni rezultati statistički su analizirani Fischerovim egzaktnim testom, Smirnov-Kolmogorovljevim i Mann-Whitney U testom uz razinu značajnosti od 0,05. Rezultati su pokazali značajno smanjenje volumena u svim ispitivanim skupinama, i to: PDT/AH+ 79,72% (p<0,05), PDT/BIO 89,58% (p<0,05), UAI/AH+ 86,98% (p<0,05), i UAI/BIO 86,95% (p<0,05). Između ispitivanih skupina nije bilo statistički značajne razlike u smanjenju volumena: PDT/AH+ i PDT/BIO (p=0,784), UAI/AH+ i UAI/BIO (p=0,458), PDT/BIO i UAI/BIO (p=0,458), PDT/AH+ i UAI/AH+ (p=0,970). Fotodinamska terapija nije pokazala superiornost u kliničkim uvjetima u odnosu na ultrazvučno aktiviranu irigaciju kao ni primijenjeni biokeramički materijal u odnosu na punilo temeljeno na epoksi smoli, kako u smanjenju periapikalne lezije, tako i u pojavnosti i intenzitetu postoperativne boli.Aim: The aim of the clinical study was to examine the effect of photodynamic therapy (PDT) and bioceramic root canal filling on periapical lesion healing. Also, the influence of PDT and bioceramic filling on the occurrence and intensity of postoperative pain after a single visit endodontic treatment was examined.
Materials and methods: The study included patients with signs and symptoms of chronic apical periodontitis who required revision, according to the inclusion and exclusion criteria. Patients were divided into two basic groups depending on the type of final root canal disinfection protocol: Group 1. Ultrasonically activated irrigation (UAI) EDTA and 3% NaOCl + PDT (diode laser 660 nm, 100 mW); Group 2. Ultrasonically activated irrigation (UAI) EDTA and 3% NaOCl. In each group, half of the root canals samples were filled with bioceramic filling BioRoot RCS (BioRoot RCS, Septodont, Saint-Maur-des-Fossés, France), and the other half of the samples with epoxy resin-based filling AH Plus (AH Plus, Dentsply, Sirona, Charlotte, USA). Radiological volumetric assessment of periapical lesion healing was done by CBCT analysis by obtaining the exact lesion volume preoperatively and one year after revision. The randomization process was conducted using the Wheel Decide program (www.wheeldecide.com). The study was single-blinded, meaning that the patients were unaware of the group to which they were allocated. The clinical procedures were standardized for both groups. Root canal retreatment was performed under local anesthesia (Articain 4% with Epinephrine 1:100,000, one ampoule, Ubistesin™ forte, 3 M ESPE, Germany) and rubber dam isolation. The traditional access opening was performed under rubber dam isolation. All caries was removed using pearshaped diamond and round carbide burs under water coolant. In cases where there was a significant loss of coronal tooth structure, class I cavities were reconstructed using a composite material (Clearfill Majesty ES2 Classic, Kuraray America, Inc. Suite, USA). The working field was disinfected with 5% NaOCl. The root canal retreatment was performed with Rendo 1, 2, and 3 rotary files (MICROMEGA, Cedex, France) using an endomotor set at 300 rpm and 200 Ncm, according to the manufacturer's recommendations. During retreatment, the root canals were irrigated with 3% NaOCl (30 G needle, Steri Irrigation Tips, DiaDent; Netherlands). The retreatment was considered complete when no signs of remaining guttapercha were visible on the instruments or in the canal. The working length was determined and measured using a Kfile size #10 or #15 up to the apical foramen (value 0 on the apex locator) on Dualpex apex locator (MICROMEGA, Cedex, France). The canals were then instrumented up to the apical foramen using 2Shape 1 and 2 instruments (2Shape, MICROMEGA, Cedex, France) and 5 ml of 3% NaOCl per canal. Endomotor setup was 300 rpm and 200 Ncm. The presence of clean dentinal shavings, clear irrigant, and glassy smooth walls were the preferred indicators of adequate cleaning of the root canals. Additionally, apical cleaning was confirmed when clean dentinal debris was present at the tip of the rotary instrument.
After completion of instrumentation, the final disinfection protocol included: irrigation with 3 ml of 3% NaOCl for 30 s, followed by 3 ml of 15% ethylenediaminotetraacetic acid (EDTA) activated for 60 s, and finally, 3 ml of 3 % NaOCl activated for 30 s. All passive irrigation was performed using 30 G needle (30 G needle, Steri Irrigation Tips, DiaDent; Netherlands) and a 2 ml syringe. After each irrigation step and before the next irrigant, the excess irrigant in the root canal was aspirated using 30 G needle and a syringe.In Group 1 (UAI), EDTA and NaOCl irrigants in the final disinfection protocol were constantly activated using an EndoUltra device (MICROMEGA, Cedex, France) with an ultrasonic noncutting tip placed at 3 mm from the working length. The irrigant was delivered into the root canal, and the ultrasonic device was constantly activated, 30 s for NaOCl and 60 s for EDTA. During activation, irrigants were constantly delivered using 30 G needle and a syringe. In both groups the irrigants were activated in the same manner as explained but with the additional application of photodynamic therapy (PDT) after irrigation in Group 1. The PDT as applied using an HF diode laser (diode laser 660 nm, 100 mW 60 s/root canal, LASER HF COMFORT; HAGER&WERKEN, Duisburg, Germany) set at continuous mode. First, the PS, Toluidine blue (HF EndoPDT solution, Hager&Werken) was applied in the root canal and
distributed along the dentinal walls using a sterile hand Kreamer size #15. The dye was left in the canal for 60 s, then removed by rinsing the canal with 2 ml of sterile saline solution and dried with sterile paper points. Finally, the root canals were irradiated using a fiber tip (320 µm diameter), placed initially 2 mm from the working length, and then moved rotationally for 60 s with rotational motion from the apical to the coronal direction. In the same session, the root canals were obturated using an epoxy resinbased sealer (AH Plus, Dentsply Sirona, Germany) or bioceramic sealer (BioRoot RCS, Septodont, SaintMaurdesFossés, France) and guttapercha cones (MICROMEGA, Cedex, France) using a singlecone
obturation technique. The access cavity was temporarily sealed with a glass ionomer (Fuji IX; GC Corporation, Tokyo, Japan). Every patient received a visual analogue scale (VAS) questionnaire to record occurrence and pain intensity immediately after the retreatment and during the following seven days and analgesic consumption. The protocol was finished seven days after revision with permanent composite filling (Clearfill Majesty ES2 Classic, Kuraray America, Inc. Suite, USA).
Results: Results showed significant periapical lesion volume reduction in all groups: PDT/AH+ 79,72% (p<0,05), PDT/BIO 89,58% (p<0,05), UAI/AH+ 86,98% (p<0,05), i UAI/BIO 86,95% (p<0,05). There were no significant differences between the groups in terms of reduction of periapical lesion volume: PDT/AH+ vs PDT/BIO (p=0,784), UAI/AH+ vs UAI/BIO (p=0,458), PDT/BIO vs UAI/BIO (p=0,458), PDT/AH+ vs UAI/AH+ (p=0,970). Additional use of PDT after UAI did not contribute to the healing of periapical lesions. The intensity of postoperative pain was highest on the first day, but considering the median VAS values, this pain was minimal (median in the range from 0 to 1). Significant differences were recorded only in one comparison - UAI/AH+ and UAI/BIO on the fourth day (P=0.049), but this difference was also not clinically significant
because the median VAS was 0, while the difference related only to the measured ranges of minimum and maximum VAS values. In conclusion, the pain was of low intensity and equal between the groups.
Conclusion: The analysis showed that there was no statistically significant difference between the examined groups, photodynamic therapy did not show superiority in clinical conditions in relation to ultrasound-activated irrigation, nor did the applied bioceramic material in relation to filler based on epoxy resin
ULOGE AUGMINA I AKTINA UNUTAR DIOBENOG VRETENA U KONGRESIJI KROMOSOMA, ARHITEKTURI VRETENA I VJERNOSTI MITOZE
No full textThe human mitotic spindle is made of microtubules nucleated at centrosomes, at kinetochores, and from pre-existing microtubules by the augmin complex. Recently, spindle actin also emerged as a possible player in spindle assembly. However, it is unknown how augmin-mediated nucleation affects distinct microtubule classes, what the spatial distribution of spindle actin and microtubules is, and, finally, what the roles of these two proteins are in spindle architecture and mitotic progression. Here, by using superresolution microscopy and cutting edge live-cell imaging, I found that augmin promotes mitotic fidelity by generating assemblies consisting of bridging and kinetochore fibers that align sister kinetochores to face opposite poles, thereby preventing erroneous attachments. Furthermore, I showed that spindle actin, by forming fine filaments in the polar region and along spindle microtubules, promotes spindle pole focusing and bipolar cell division.Mikrotubuli diobenog vretena se u ljudskim stanicama nukleiraju na centrosomu, kinetohorama te na površini već postojećih mikrotubula pomoću augminskog kompleksa. Nedavno je predloženo da i aktin unutar diobenog vretena ima ulogu u njegovom sastavljanju. Međutim, još uvijek nije poznato na koji način nukleacija pomoću augmina utječe na različite klase mikrotubula, koja je prostorna raspodjela aktina i mikrotubula unutar vretena te koja je uloga ova dva proteina u arhitekturi vretena i progresiji mitoze. Koristeći superrezolucijsku mikroskopiju te najnoviju tehnologiju snimanja živih stanica pokazala sam da augmin ima ulogu u pravilnoj podjeli kromosoma. Augmin stvara sklopove mikrotubula koji se sastoje od premošćujućih i kinetohornih vlakana što poravnava sestrinske kinetohore na način da su okrenute prema suprotnim polovima, te tako sprječava pogrešna vezanja s mikrotubulima. Nadalje, pokazala sam da aktin unutar vretena promiče fokusiranje polova vretena te bipolarnu mitozu tako što formira filamente u polarnoj regiji te uzduž mikrotubula
Teorijski dizajn novih materijala za iskorištavanje sunčeve energije
No full textThe subject of the thesis is development of novel nanoscale materials for solar energy harvesting. The aim is to theoretically design two types of new luminescent dyes with enhanced efficiency: the first for application in dye-sensitized solar cells (DSSCs) and the second for use in transparent luminescent solar concentrators (TLSCs). More precisely, the objective is to predict photovoltaic and photochemical properties, including energy conversion efficiency and fluorescence quantum yield (QY). The first research direction focuses on novel bio-nano hybrid sensitizers for use in dye-sensitized solar cells, specifically on cyanidin-silver nanocluster hybrids. Furthermore, the influence of odd and even numbers of electrons and the impact of gold or copper doping on the efficiency and stability of these hybrids are investigated. The second research direction emphasises developing the rules for reliable theoretical prediction of fluorescence quantum yield within harmonic approximation. Additionally, it involves the theoretical design of squaraine-based J-aggregates as transparent TLSC luminophores with high QY. The calculations of structural and optical properties are based on density functional theory (DFT) and its time-dependent variant (TDDFT). Overall, the theoretical modeling of photovoltaic and photochemical properties serves to confirm and to stimulate experimental research in the field of new solar technologies.Teza istražuje razvoj novih nanomaterijala za prikupljanje solarne energije. Cilj je teoretski dizajnirati dvije vrste novih luminescentnih boja s poboljšanom učinkovitošću: jedne za primjenu u bojom senzibiliziranim solarnim ćelijama (DSSC), a druge za primjenu u transparentnim luminiscentnim solarnim koncentratorima (TLSC). Glavni cilj je predviđanje fotovoltaičnih i fotokemijskih svojstava, kao što su efikasnost fotoelektrične pretvorbe i efikasnost svjetlosne emisije (QY). Teza se sastoji od dva smjera istraživanja. Prvi smjer istraživanja stavlja u fokus nove hibridne bio-nano senzibilizatore za primjenu u DSSC sustavima, posebice hibridne cijanidin-srebrne nanoklastere. Nadalje, prikazan je utjecaj na učinkovitost i stabilnost bio-nano hibrida kroz istraživanje parnog i neparnog broja elektrona te dopiranja zlatom ili bakrom. Drugi smjer istraživanja bavi se razvojem pravila za pouzdano teoretsko predviđanje efikasnosti svjetlosne emisije (fluorescentni QY) unutar harmonijske aproksimacije. Dodatno, uključuje teoretski dizajn J-agregata na bazi skvaraina kao prozirnih TLSC luminofora s visokim fluorescentnim QY. Izračuni strukturnih i optičkih svojstava temelje se na teoriji funkcionala gustoće (DFT) i njenoj vremenski ovisnoj varijanti (TDDFT). Teorijsko modeliranje fotovoltaičnih i fotokemijskih svojstava služi za potvrdu i stimulaciju eksperimentalnih istraživanja u području novih solarnih tehnologija