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    Utilizing machine learning for analysis of geometry in CAD models of dental individual abutments

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    Dentalne nadogradnje su komponente koje se koriste u dentalnoj implantologiji. One se pričvršćuju na dentalni implantat ugrađen u kost lubanje ili čeljusti pacijenta, a protetski nadomjestak se zatim pričvršćuje na nadogradnju. Na uspješnost implantološke terapije utječe svaka korištena komponenta, pa tako i dentalna nadogradnja. Individualne dentalne nadogradnje, prilagođene pojedinačnim pacijentima, pokazuju bolja mehanička svojstva i dosjedanje na zubno meso od standardiziranih, konfekcijskih nadogradnji. Za bolje razumijevanje uspješnosti terapija s individualnim dentalnim nadogradnjama važno je analizirati njihovu geometriju radi boljeg razumijevanja značaja njihove geometrije. Nenadziranim strojnim učenjem može se analizirati geometrija individualnih dentalnih nadogradnji bez ljudske pristranosti. Iako je strojno učenje uspješno implementirano u različitim područjima, njegova primjena na 3D modelima je i dalje ograničena zbog neujednačene diskretizacije podataka i manjka označenih skupova podataka. 3D modeli su uobičajeno opisani oblakom točaka ili mrežastim modelima, a strojno učenje se često radi s voxel modelima zbog ujednačene diskretizacije podataka. Individualne dentalne nadogradnje pogodni su kandidati za analizu nenadziranim strojnim učenjem kako bi se pojednostavio proces konstruiranja. Ovaj rad primjenjuje nekoliko ML metoda za analizu geometrije individualnih dentalnih nadogradnji koristeći nenadzirano učenje s voxel modelima nadogradnji. Korištene su tri metode strojnog učenja bez nadzora: K-Means za segmentaciju, konvolucijski autoenkoder za rekonstrukciju i kodiranje, te analiza glavnih komponenti i K-Means za klasifikaciju individualnih dentalnih nadogradnji. K-Means je učinkovito segmentirao nadogradnje u dijelove, ali je imao poteškoća sa širim koronalnim dijelovima. Analiza glavnih komponenata i K-Means su identificirali važne značajke individualnih dentalnih nadogradnji, te su ih klasificirali u šest kategorija. Konvolucijski autoenkoder je generirao kodiranu reprezentaciju od 16 vrijednosti, što je omogućilo klasifikaciju, ali je kvaliteta rekonstrukcija varirala. Individualne dentalne nadogradnje pretkutnjaka i kutnjaka imaju bolje rekonstrukcije od nadogradnji sjekutića i očnjaka. Ovi rezultati pokazuju potencijal za automatizaciju označavanja i pojednostavljenje konstruiranja individualnih dentalnih nadogradnji nenadziranim strojnim učenjem.Dental abutments are components used in dental implantology. They attach to a dental implant embedded in the patient's skull or jawbone, and a prosthetic restoration is then attached to the abutment. Each component used in implantology, including dental abutments, affects the success of implant therapy. Custom dental abutments, tailored to individual patients, exhibit better mechanical properties and fit compared to standardised, stock abutments. Analysing the geometry of custom dental abutments is a crucial step in achieving a better understanding of how the geometry affects therapeutic success. Unsupervised machine learning can analyse the geometry of custom dental abutments without human bias. Although machine learning has been successfully implemented in various fields, its applications with 3D models remain limited due to irregular data discretisation and insufficient labeled datasets. 3D models are typically described by point clouds or meshes, but machine learning often works with voxel models due to their uniform data discretisation. Custom dental abutments are suitable candidates for analysis using unsupervised machine learning to simplify their design process. This study applies several unsupervised machine learning methods to voxel models of custom dental abutments in order to analyse their geometry. Three unsupervised machine learning methods were used: K-Means for segmentation, a convolutional autoencoder for reconstruction and encoding, and principal component analysis combined with K-Means for the classification of custom dental abutments. K-Means effectively segmented abutments into sections but struggled with wider coronal sections. Principal component analysis combined with K-Means identified important features of custom dental abutments and classified them into six categories. The convolutional autoencoder generated a 16-value encoded representation, enabling classification, though the quality of reconstructions varied. Custom abutments for premolars and molars had better reconstructions than those for incisors and canines. These findings indicate the potential for automating the labelling and simplifying the design of custom dental abutments through unsupervised ML

    Vodorazrjedivi premazi za zaštitu brončane kulturne zaštite

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    Objects of tangible cultural heritage, such as sculptures, are often made of bronze and located outdoors where they are directly exposed to the corrosive effect of precipitation, humidity, sunlight, temperature and airborne contaminants. To protect them organic coatings, varnishes and waxes are used that meet the requirements of the conservation profession. However, in recent decades, legislations were enacted with an aim to restrict the use of coatings with high content of volatile organic compounds due to their toxicity and negative impact on the environment and human health. For this reason, efforts are being made in all branches of industry to replace solventborne with waterborne coatings, in which the content of organic solvents is reduced and replaced by water. However, waterborne coatings still offer weaker protection than solventborne coatings under similar conditions. For that reason, different approaches to improve their performance are examined. The aim of this thesis was to investigate the applicability of industrial waterborne coatings for corrosion protection of bare and patinated bronze surfaces and the possibility of enhancement of their corrosion protection efficiency and adhesion by surface pretreatment with long-chain phosphonic acids. Sculptures made of bronze are artificially patinated before protective coating application and exposure to the outdoor environment. This artificially formed patina is very reactive, so it was necessary to study its behavior before applying the protection. Artificial sulphide patina was formed on various bronze substrates (CuSn12, CuSn6, RG7) used in the production of bronze sculptures. The corrosion behaviour of the patina was investigated by electrochemical methods, in different corrosive environments: artificial urban and acid rain as well as in NO2 rich atmosphere, with alternating wet and dry cycles. The morphology and composition of the samples were analyzed using microscopic (SEM) and spectroscopic (FTIR) techniques. It was found that the patina undergoes transformation when exposed to a corrosive medium, increasing its resistance and corrosion stability. This entire process depended significantly on the duration of wet period and corrosivity of medium, while the bronze substrate composition was less important factor. Since waterborne coatings contain water, which is less volatile than organic solvents, it was necessary to study the influence of temperature and duration of the drying process on coating final properties. In the first step, conducting tests with an industrial coating, containing a corrosion inhibitor, enabled the selection of suitable coating application parameters. Then, additional waterborne coating was selected, which does not contain corrosion inhibitor, and both coatings were applied on differently patinated bronze substrates, as well as on bare bronzes. Although both coatings proved to be effective, the coating containing corrosion inhibitor showed slightly higher level of corrosion protection and was selected for further studies. It is important to emphasize that this coating does not change the visual appearance of the surface either during application or after exposure to a corrosive environment, as required by conservation ethics. In the next step, the possibility of improvement of waterborne coating corrosion protection and adhesion on bare and patinated bronzes was examined. For this purpose surface pre-treatment with long-chain phosphonic acid was applied. The level of corrosion protection of bare and artificially patinated bronze was tested by electrochemical measurements (polarization measurements and electrochemical impedance spectroscopy) under conditions of simulated acid rain (pH 5) or NO2 atmosphere. The adhesion of the coating to the metal substrate was tested using the pull-off method. It was found that 12- aminododecylphosphonic acid, when applied on bronze by immersion in ethanolic solution, can act as a corrosion inhibitor, as well as a coating adhesion promoter. The research was extended to two other phosphonic acids that differ in chain length and terminal group. Furthermore, all three acids were applied by the brush method in addition to the immersion, which would be more suitable in the practice of cultural heritage. It has been shown that certain improvements can be achieved with both methods, which are more pronounced on a bare surface than on a patinated surface, which is quite porous and reactive. The arrangement of the phosphonic acid films was analyzed by goniometry and the correlation between phosphonic film crystallinity and its effect on coating properties was observed. In summary, it has been shown that industrial waterborne acrylic coatings can effectively protect bare and patinated bronzes, even if the level of protection does not reach the level of similar solventborne coatings. It has been shown that pretreatment with appropriate phosphonic acid can improve the protective properties and adhesion of such coating.Objekti materijalne kulturne baštine, poput skulptura, često su izrađeni od bronce i nalaze se na otvorenom gdje su izravno izloženi korozivnom djelovanju oborina, vlage, sunčeve svjetlosti, temperature i onečišćenja iz zraka. Za njihovu zaštitu koriste se organski premazi, lakovi i voskovi koji zadovoljavaju zahtjeve konzervatorske struke. Posljednjih desetljeća doneseni su zakoni kojima se ograničila uporaba premaza s visokim udjelom hlapivih organskih spojeva zbog njihove toksičnosti i negativnog utjecaja na okoliš i zdravlje ljudi. Zbog toga se u svim granama industrije premazi na bazi otapala nastoje zamijeniti premazima na bazi vode u kojima je sadržaj organskih otapala smanjen i zamijenjen vodom. Međutim, premazi na bazi vode i dalje pružaju slabiju zaštitu od premaza na bazi otapala pod sličnim uvjetima. Zbog toga se istražuju pristupi za poboljšanje njihove učinkovitosti. Cilj ovog doktorskog rada bio je istražiti primjenjivost industrijskih vodorazrjedivih premaza u svrhe korozijske zaštite čistih i patiniranih brončanih površina te mogućnost unaprjeđenja učinkovitosti njihove zaštite i adhezije površinskom predobradom dugolančanim fosfonskim kiselinama. Skulpture izrađene od bronce umjetno se patiniraju prije nanošenja zaštitnog premaza i izlaganja vanjskom okolišu. Ova umjetno stvorena patina je vrlo reaktivna te je bilo potrebno proučiti njeno ponašanje prije nanošenja zaštite. Umjetna sulfidna patina formirana je na različitim brončanim podlogama (CuSn12, CuSn6, RG7) koje se koriste u izradi brončanih skulptura. Korozivno ponašanje patine istraženo je elektrokemijskim metodama u različitim korozivnim okolišima: umjetna urbana i kisela kiša, kao i u atmosferi bogatoj NO2 s izmjeničnim vlažnim i suhim ciklusima. Morfologija i sastav uzoraka analizirani su mikroskopskom (SEM) i spektroskopskom (FTIR) tehnikom. Utvrđeno je da se patina transformira kada je izložena korozivnom mediju gdje dolazi do porasta njene otpornosti i korozijske stabilnosti. Cijeli ovaj proces značajno je ovisio o trajanju vlažnog razdoblja i korozivnosti medija dok je sastav brončane podloge bio manje bitan faktor. Budući da vodorazrjedivi premazi sadrže vodu, koja je manje hlapiva od organskih otapala, bilo je potrebno istražiti utjecaj temperature i trajanja procesa sušenja na konačna svojstva premaza. U prvom koraku provođenje testova s industrijskim premazom, koji sadrži inhibitor korozije, omogućilo je odabir odgovarajućih parametara nanošenja premaza. Zatim je odabran dodatni vodorazrjedivi premaz koji ne sadrži inhibitor korozije te su oba premaza nanesena na različito patinirane brončane podloge kao i na gole bronce. Iako su se oba premaza pokazala učinkovitima, premaz koji je sadržavao inhibitor korozije pokazao je nešto višu razinu korozijske zaštite te je odabran za daljnja istraživanja. Važno je naglasiti da ovaj premaz ne mijenja vizualni izgled površine niti tijekom nanošenja niti nakon izlaganja korozivnoj okolini što je u skladu s konzervatorskom etikom. U sljedećem koraku ispitana je mogućnost poboljšanja korozijske zaštite i adhezije vodorazrjedivog premaza na čistoj i patiniranoj bronci. U tu svrhu primijenjena je predobrada površine dugolančanom fosfonskom kiselinom. Razina korozijske zaštite čiste i umjetno patinirane bronce ispitana je elektrokemijskim mjerenjima (polarizacijska mjerenja i elektrokemijska impedancijska spektroskopija) u uvjetima simulirane kisele kiše (pH 5) ili atmosfere NO2. Adhezija premaza na metalnu podlogu ispitana je pull-off testom. Utvrđeno je da 12-aminododecilfosfonska kiselina, kada se nanese na broncu uranjanjem u etanolnu otopinu, može djelovati kao inhibitor korozije te kao promotor adhezije premaza. Istraživanje je prošireno na dvije druge fosfonske kiseline koje se razlikuju po duljini lanca i terminalnoj skupini. Nadalje, sve tri kiseline su uz metodu uranjanja nanesene i metodom kista koja bi bila prikladnija u praksi za kulturnu baštinu. Pokazalo se da se objema metodama mogu postići određena poboljšanja koja su izraženija na čistoj nego na patiniranoj površini budući da je ona dosta porozna i reaktivna. Uređenost filmova fosfonskih kiselina analizirana je goniometrijom te je proučavana korelacija između kristalnosti filma fosfonske kiseline i njezinog učinka na svojstva premaza. U konačnici, pokazalo se da industrijski, vodorazrjedivi akrilni premazi mogu učinkovito zaštititi čistu i patiniranu broncu čak i ako razina zaštite ne doseže razinu zaštite sličnih organskih premaza. Pokazalo se da prethodna obrada odgovarajućom fosfonskom kiselinom može poboljšati zaštitna svojstva i adheziju takvog premaza

    Multiple-effect evaporation plant with steam jet thermocompressor

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    U diplomskom radu prikazane su karakteristike soka od naranče i procesa prerade. Navedena je i opisana karakteristična oprema koja se koristi u procesu ugušćivanja (uparivanja, koncentracije) narančinog soka. Proveden je potpuni termodinamički proračun višestupanjskog postrojenja za koncentraciju soka od naranče s početne koncentracije 12% na konačnu koncentraciju 60%. Proračunata su sva četiri stupnja uparivanja, termokompresor, dva predgrijača, pasterizator i kondenzator. Proračunate su potrebne ogrjevne površine uparivačkih stupnjeva te je proveden proračun čvrstoće posljednjeg uparivačkog stupnja. U prilogu rada nalaze se tehnički crteži posljednjeg stupnja uparivanja i izrađena procesno-instrumentacijska shema postrojenja (P&ID)As part of the master's thesis, the characteristics of orange juice and orange juice evaporation process are given. Various equipment used in the evaporation process is described. A complete thermodynamic calculation of a multiple-effect orange juice evaporation plant used for concentrating orange juice from 12% to 60% is conducted. This includes: four falling film evaporators, an ejector (thermocompressor), two juice preheaters, a pasteurizer and a condenser. Heat transfer calculations which result in the required surfaces for heat exchange in the evaporators are shown, alongside a stress calculation of the final evaporator stage. In the appendix, engineering drawings of the final effect evaporator and the P&ID of the plant are given

    Heavy metals in formulated dietary supplements for the treatment of inflammatory bowel diseases

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    Upalne bolesti crijeva su teške bolesti s nuspojavama koje utječu na svakodnevni život pacijenata koji od njih boluju. Mnogi uz standardnu farmakoterapiju uzimaju i razne dodatke prehrani. Među njima su i biljni pripravci kurkume, justicije i indijskog tamjanovca koji se koriste za ublažavanje simptoma upalnih bolesti crijeva. Osim bioaktivnih molekula koje se prirodno nalaze u ovim biljkama i koje pokazuju farmakološki učinak, mogu se naći i razna onečišćenja kao naprimjer teški metali.. Teški metali nemaju fiziološku funkciju u ljudskom tijelu i osim toga imaju potencijal biti iznimno toksični. U ovom radu se određivao sadržaj olova, arsena i cinka u 12 dodatak prehrani s ciljem procjene sigurnosti njihove primjene.. Koncentracija metala je određena atomskom apsorpcijskom spektrometrijom grafitnom tehnikom nakon prvotne mikrovalne digestije uzoraka. Izračunata je količina teških metala koja bi se unijela u jednoj dozi i dnevno prateći upute proizvođača i od 12 uzoraka jedan od njih prelazi dozvoljeni dnevni unos za olovo prema ICH smjernicama. U pripravcima su dokazane varijabilne koncentracije teških metala što ukazuje na potrebu temeljite kontrole sigurnosti ovakvih dodataka prehrani.Inflammatory bowel diseases are crippling diseases that have a severe impact on the everyday life of its patients. Many such patients take various dietary supplements in addition to their standard pharmacotherapy. Among them exist herbal supplements based on turmeric, green chiretta and Indian frankincense which are used to alleviate the symptoms of inflammatory bowel diseases. In addition to the bioactive molecules that are naturally found in these plants and that show a pharmacological effect, various pollutants can be found, such as heavy metals. Heavy metals have no physiological function in the human body and, in addition, have the potential to be extremely toxic. In this study, the content of lead, arsenic and zinc in 12 dietary supplements was determined with the aim of assessing the safety of their use. Metal concentration was determined by atomic absorption spectrometry using the graphite technique after initial microwave digestion of the samples. The amount of heavy metals that would be ingested in a singular and daily dose following the recommended intake by the manufacturer was calculated, and out of 12 samples, one of them exceeded the permitted daily intake for lead according to ICH guidelines. Variable concentrations of heavy metals have been proven in the preparations, which indicates the need for thorough control of the safety of such dietary supplements

    Gaseous substances as lubricants

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    Plinovi imaju primjenu kao sredstva za podmazivanje baš poput konvencionalnih (kapljevitih) i krutih maziva, ali im je učestalost ipak manja zbog nekih od svojstva plinova. Primjerice, neki plinovi su skupi pa je samim time dostupnost i učestalost primjene manja, iako su ostala svojstva kvalitetna. Najčešći plin za podmazivanje je zrak, a neki od uređaja u kojima se koristi ova vrsta ležajeva su turbomotori, žiroskopi (gyroskopi) te precizni optički uređaji poput nekih teleskopa i mikroskopa. Naveden je i primjer stomatološke bušilice kao jednog od najpoznatijih uređaja u kojima se koristi zračni ležaj. U ovom radu prikazani su neki primjeri, opisana su svojstva plinova i način funkcioniranja kliznog ležaja te stvaranje hidrodinamičkog sloja u mazivom filmu.Gases are used as lubricants just like conventional (liquid) and solid lubricants, but their frequency is still lower due to some of the properties of gases. For example, some gases are expensive, so their availability and frequency of application is lower, even though the other properties are of good quality. The most common lubricating gas is air, and some of the devices in which this type of bearing is used are turbomotors, gyroscopes and precise optical devices such as some telescopes and microscopes. An example of a dental drill is given as one of the most famous devices in which an air bearing is used. This thesis presents some examples, describes the properties of gases and the way the sliding bearing functions, as well as the creation of a hydrodynamic layer in the lubricating film

    Velika sportska događanja kao pokretač razvoja turizma destinacija

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    Sportska događanja postaju sve popularnija. Tijekom posljednjeg desetljeća broj posjećenosti na sportskim događanjima se drastično povećao. Ljudi su spremni proputovati puno kilometara samo kako bi prisustvovali na njima. Upravljanje sportskim događanjima može se povezati s turizmom jer obje djelatnosti proizlaze iz želje pojedinca za kvalitetno ispunjenim slobodnim vremenom i zadovoljavanjem određenih potreba. U radu su navedene brojne studije i istraživanja vezane za sportski turizam i velika sportska događanja poput Svjetskog prvenstva ili Olimpijskih igara

    Epigenetic status and expression of SALL4 in normal and impaired testicular development

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    Uloga gena SALL4, koji kontrolira razvoj spermatogonija, nije dovoljno istražena u razvoju sjemenika sisavaca, a u neplodnosti čovjeka je potpuno neistražena. Cilj disertacije bio je analizirati izražaj Sall4/SALL4 u razvoju sjemenika štakora in vivo i in vitro te u ljudskim sjemenicima s različitim dijagnozama neopstruktivne azoospermije (NOA) in vivo, kao i njegov metilacijski status u in vivo uzorcima. Pirosekvenciranjem je pokazano da je SALL4/Sall4 uvijek hipometiliran u sjemeniku. qRT-PCR-om je pokazan značajno veći izražaj Sall4 mRNA u fetalnom štakorskom sjemeniku nego u postnatalnom; a u ljudskim sjemenicima sa sindromom samo Sertolijevih stanica (SCOS) SALL4 mRNA je snižena u odnosu na hipospermatogenezu (HS) i zastoj u sazrijevanju (MA). Osim u spermatogonijama, poboljšanim IHC i IF protokolima je po prvi put pokazan SALL4 u XY tjelešcu primarnih spermatocita. Također, pokazan je pojačan izražaj SALL4 u pre-pahitenskim spermatocitama i citoplazmi intersticijskih stanica u neplodnom sjemeniku u odnosu na zdravi i HS sjemenik čovjeka. Nadalje, uspostavljen je novi 3D in vitro sustav za uzgoj tkiva sjemenika štakora, a primjena siRNA snizila je izražaj Sall4 na mRNA (za 42 %) i proteinskoj razini uzrokujući smanjeni rast i narušenu histologiju. Ovi rezultati ukazuju na SALL4 kao novi potencijalni biljeg u dijagnostici NOA te podrobnije rasvjetljavaju njegovu ulogu u procesu spermatogeneze.The role of the SALL4 gene which controls the development of spermatogonia, has been insufficiently investigated in the development of the mammalian testis, and is completely unexplored in human infertility. The doctoral thesis aimed to analyze the expression of Sall4/SALL4 in the rat testis development in vivo and in vitro as well as in the human testis with a different diagnosis of nonobstructive azoospermia (NOA) and its DNA methylation status. The pyrosequencing showed that SALL4/Sall4 is always hypomethylated in the testis. The qRT-PCR has shown significantly higher expression of the Sall4 mRNA in fetal rat testis than in postnatal; while SALL4 mRNA was lower in human testis with Sertoli cell only syndrome (SCOS) than in hypospermatogenesis (HS) and maturation arrest (MA). Except in spermatogonia, improved IHC and IF protocols showed the expression of the SALL4 protein in the XY body of primary spermatocytes of human testes. Also, increased expression of SALL4 in pre-pachytene spermatocytes and cytoplasm of interstitial cells in infertile compared to healthy human testis was demonstrated. Furthermore, an original 3D in vitro system for the cultivation of rat testis tissue was established, and the application of siRNA decreased Sall4 at the mRNA (by 42 %) and protein levels, causing reduced growth and impaired histology. These results indicate SALL4 as a new potential marker in the diagnosis of NOA and shed more light on its role in the process of spermatogenesis

    Sadržaj metala u eluatima tla s područja bivše tvornice glinice kod Obrovca i njihov učinak na klijanje sjemenki salate (Lactuca sativa)

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    Alumina factories are plants for refining aluminum oxide from bauxite ore. Seven soil samples were taken in the vicinity of the former Jadral alumina factory near Obrovac, and the multielement analyses revealed elevated concentrations of heavy metals, especially iron (Fe), but high levels of Mn, Cr, V and Zn were also detected. Two types of soil eluates were prepared from the soil samples using two methods - the EN 12457-2 (European Standard Batch Leaching Test) and the TCLP-2 (Toxicity Characteristic Leaching Procedure). The soil eluates differed mainly in the pH values, while the metal content was generally low. The seed germination test was carried out not only with soil eluates prepared according to the two methods mentioned, but also with eluates whose pH was adjusted to 6.5. In addition to the influence of multielement composition of the eluates, the pH value had a predominant effect on both the germination of the lettuce seeds and the radicle growth. Comparing the effects of the samples on radicle growth and the germination process, radicle growth was the more sensitive parameter. This study sheds light on the impact of the former alumina factory, by showing the presence of heavy metals in the soil and possible consequences for the environment.Tvornice glinice su postrojenja za rafiniranje aluminijevog oksida iz boksitne rude. U sklopu ovog istraživanja uzeto je sedam uzoraka tla u blizini bivše tvornice Jadral kod Obrovca. Multielementna analiza otkrila je povišene koncentracije teških metala u tim uzorcima, posebice željeza (Fe), kao i visoke razine Mn, Cr, V i Zn. Kako bi se detaljnije istražili ovi nalazi, dvije vrste eluata tla pripremljene su iz uzoraka tla korištenjem dviju različitih metoda - EN 12457-2 (European Standard Batch Leaching Test) i TCLP-2 (Toxicity Characteristic Leaching Procedure). Dobiveni eluati tla razlikovali su se prvenstveno u pH vrijednosti, dok je njihov sadržaj metala općenito bio nizak. Uz navedeno, istražen je utjecaj eluata na klijavost sjemenki salate, ne samo eluata tla pripremljenih prema gore navedenim metodama, već i eluata čija je pH vrijednost podešena na 6,5. Rezultati su pokazali da je uz multielementni sastav uzoraka eluata tla, značajan bio utjecaj pH vrijednosti, kako na klijavost sjemenki salate tako i na rast korijenka. Uspoređujući učinke uzoraka na rast korijenka i proces klijanja, rast korijenka bio je osjetljiviji parametar. Ovo istraživanje ukazuje na utjecaj bivše tvornice aluminija, ističući prisutnost teških metala u tlu i moguće posljedice za okoliš

    Genetic and population characteristics of stone crayfish Austropotamobius torrentium (Schrank, 1803) in Sušik cave

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    Potočni rak, Austropotamobius torrentium (Schrank, 1803), autohtona je i najmanja vrsta slatkovodn ih deseteronožnih rak ova u Europi i prioritetna vrsta Europske unije. P odručje sjevernih centralnih Dinarida , uključujući Hrvatsku , prepoznato je kao centar raznolikosti vrste Cilj rada bio je istražiti genetske i populacijske značajke neistražene populacije ponora Sušik , jednog od rijetkih nalaza ove vrste u podzemlju . U razdoblju od srpnja do listopada populacija na početnom dijelu ponora je istražena metodo m označavanja i ponovnog ulova . Svakoj ulovljenoj jedinki određeni su spol, dužina i težina. Kod ukupno 30 jedinki uzet je jedan pereopod za potrebe genetskih analiza. Tijekom istraživanja, ulovljena je 181, a označene 153 jedinke. Veličina populacije procijenjena je na 1,01 jedinki / m 2 . Populacija je stabilna, s ujednačenim omjerom mužjaka i ženki i stabilnom uzrasnom strukturom u kojoj su zastupljeni svi veličinski razredi. Zabilježena su odstupanja od godišnjeg ciklusa koja potencijalno pokazuju prilagodbu populacije na špiljski okoliš. Analizom mitohondrijskog gena COI , utvrđena je pripadnost populacije postojećim haplotipovima 44 i 45, te potencijalno postojanje dva nova haplotipa. Analiza osam mikrosatelitnih markera pokazala je izoliranost populacije, nepostojanje protoka gena te vel iku vrijednost privatnih alela što ukazuje na genetsku jedinstvenost populacije . Rezultati rada temelj su za buduće usporedbe podzemnih i nadzemnih populacija okolice.The stone crayfish, Austropotamobius torrentium (Schrank, 1803), is the smallest native European freshwater crayfish and a priority species on the European union’s Habitats Directive. Northern central Dinarides are recognized as its biodiversity hotspot. The aim of this study was to determine genetic and population characteristics of the stone crayfish in cave Sušik, one of its rare underground populations. Between July and October of 2023, a total of 181 individuals were caught at the mouth of cave Sušik and their sex, length and weight were measured. Of those, 153 were marked to conduct the mark and recapture method. Pereopods were removed from 30 specimens for further genetic analysis. The population is stable, with an estimated size of 1.01 individuals / m2, and with even distribution of sexes and size classes. A deviation from the usual year cycle was noted, possibly indicating an adaptation to subterranean environment. Analysis of mitochondrial COI gene placed the individuals within two existing haplotypes with the possibility of existence of two new ones. Microsatellite analysis established poor gene flow but high number of private alleles, pinpointing isolation of the studied population. The results of this thesis provide baselines for further comparisons of populations above and below ground

    Synthesis of new aromatic C-nitroso derivatives and their adsorption on gold surface

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    U ovom radu provedena je detaljna optimizacija sintetskih postupaka za pripravu novih aromatskih C-nitrozo derivata, koji sadrže funkcijsku skupinu sa sumporom koja im omogućuje adsorpciju na površinu zlata. U nekoliko reakcijskih koraka uspješno su sintetizirani i okarakterizirani bis(4-nitrozobenzil)disulfid i 1,2-bis(4-nitrozobifenil)disulfid. Aromatski C- nitrozo produkti su u posljednjem koraku sinteze pripravljeni redukcijom odgovarajućeg nitro derivata do N-hidroksilamina, koji je potom bez izolacije oksidiran do nitrozo spoja. Provedena su preliminarna istraživanja morfoloških i topografskih karakteristika molekularnih slojeva sintetiziranih aromatskih C-nitrozo derivata na površini zlata(111) uz pomoć mikroskopije atomskih sila. Dobiveni rezultati ukazuju na utjecaj specifičnih strukturnih karakteristika adsorbiranih nitrozo spojeva na njihovo samoudruživanje i dimerizaciju ili polimerizaciju na površini zlata.In this thesis, synthetic procedures for preparation of new aromatic C-nitroso derivatives containing a sulfur functional group for the adsorption on gold surface, were optimized in detail. In several reaction steps, bis(4-nitrosobenzyl)disulfide and 1,2-bis(4-nitrosobiphenyl)disulfide were successfully synthesized and characterized. The aromatic C-nitroso products were prepared in the final step of synthesis pathway by reducing the corresponding nitro derivative to N-hydroxylamine, which was then oxidized to the nitroso compound without isolation. Preliminary investigations of the morphological and topographical characteristics of molecular layers of synthesized aromatic C-nitroso derivatives on gold(111) surface were conducted using atomic force microscopy. The obtained results indicate the influence of specific structural characteristics of adsorbed nitroso compounds on their self-assembly and dimerization or polymerization on the gold surface

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