Doctor of Philosophy

dissertationAn improved method for the [2+2+2] cycloaddition of diynes with CO2 to synthesize pyrones was developed using a Ni/NHC catalyst system. The new catalyst system boasts improved yields, lower reaction temperatures, and lower reaction pressures compared to the previously known methods. Furthermore, certain unsymmetrical diynes could be employed in the reaction to generate a single pyrone regioisomer. Extensive studies suggest that the regioselectivity arises from steric interactions between the NHC ligand and the substituents on the alkyne termini. In an effort to synthesize pyrans, attempts at cyclizing aldehydes and ketones with diynes and enynes were made. When aldehydes and diynes were employed, the expected pyran cycloadduct was not obtained. Instead, the [3,3] electrocyclic ring opened tautomer was obtained. The use of enynes with aldehydes prevented this tautomerization, but the synthesis of the desired pyran was highly substrate dependent due to competitive side product formation. The use of ketones and enynes in the cycloaddition allowed for the chemoselective formation of dihydropyrans in excellent yields. However, it was necessary to carefully tune the reaction conditions to each particular substrate in order to achieve high yields. Nonetheless, this represents the first [2+2+2] cycloaddition of ketones and enynes. Due to the air sensitivity of the Ni(0) precursor and the carbene ligand, a method was devised for generating the active catalyst in situ from air stable precursors. While this method worked very well for the cyclization of diynes and nitriles, the coupling of diynes with CO2, aldehydes, and isocyanates was less successful. The Ni/NHC cycloisomerization of enynes to 1,3-dienes was also discovered. While the yields of this reaction were excellent, the substrate scope was limited. Attempts at improving the system were initiated though an in-depth study reaction mechanism. Deuterium labeling experiments suggest that the active catalyst is formed by an unprecedented C-H activation of the carbene ligand by the Ni(0)

Trauma and social work

Travmatični ter stresni dogodki so pri ljudeh zelo pogosti. Pojavljajo se na najrazličnejših področjih. Pri posamezniku se kažejo na telesni ravni, psihični ravni ter socialni ravni. Te ravni se med seboj nenehno prepletajo in so odvisne ena od druge. V svojem delu sem želela raziskati kako hud stresni oz. travmatični dogodek vpliva na osebo z vseh vidikov zgoraj zapisanih ravni, kako se oseba s hudo stisko spoprijema, kdo ji pri tem pomaga oz. kdo jo ovira k čustvenemu ter mentalnemu napredku. V svoje raziskovanje slednjega sem vpletla moč socialnega dela. Ugotavljala sem kakšne metode, tehnike ter pristope uporablja socialni delavec pri svojem delu z osebo, ki ima izkušnjo s travmatičnim, stresnim dogodkom in nenazadnje kako je v posameznikovo izkušnjo vpletena socialna mreža, tako ožja kot širša. Rezultati analize pokažejo, da človek s travmatično, stresno izkušnjo lažje premaguje svoje doživljanje ter telesna nazadovanja, če ima socialno podporo. Raziskava pokaže, da je ožja socialna mreža, tj. družina, partner, najpomembnejša pri čustvenem ter telesne napredovanju, ter obratno. Iz raziskave je razvidno, da je prav tako kot podpora ožje socialne mreže, pomembna podpora institucij, tj. osebna zdravnica, bolnišnice, centri za socialno delo na katere se oseba lahko obrne ter ob podpori slednjih pridobi neko stabilnost ter motivacijo za nove, pozitivne začetke spopadanja s svojo negativno izkušnjo. Oseba ob socialni ter institucionalni podpori pridobiva na moči, krepi svojo samozavest ter posledično razvija in krepi tehnike za kvalitetno spopadanje s svojo doživeto izkušnjo.Traumatic and stressful events are very common in people. They appears in various fields. They manifest themselves either at the physical, psychological or social levels. These levels are constantly intertwined with each other and depend on each other. In my work I wanted to explore how severe stress or a traumatic event affects a person from all aspects of the levels described above, how a person with severe distress copes with, who is helping or assisting her and who impedes her to emotional and mental progress. In my research, I also involved the power of social work. I observed what methods, techniques and approaches use social workers in their work with a person who had or has experience with a traumatic, stressful event, and finally how the individual\u27s experience involved a social network - narrower than the width. The results of the analysis show that a person with a traumatic, stressful experience can more easily overcome his or her experiencing and physical decline if he or she has social support. The research shows that the narrower social network (family, partner) is most important in emotional and physical progression, and vice versa. The survey shows that the support of institutions is also important. Personal physician, hospitals, social work centers to which a person can turn and with the support of the latter to obtain a stability and motivation for new, positive beginnings to cope with their negative experience. A person with social and institutional support is gaining strength, she enhances her self-esteem and, consequently, develops and strengthens coping techniques for quality of her life and mental health

Development and analysis of methods for GPS carrier phase double differences forming

In this thesis various methods of reference satellite determination, used for carrier phase double differences forming are tested and analyzed. First, the theoretic introduction is made to enlighten the scope of our research. Hereinafter our research on finding and programming the optimal method for reference satellite determination using Dijkstra’s algorithm is presented. The method is based on theoretical assumptions found in literature. Whole research process and programs made to implement our method are described in details. In the second part of the thesis we perform a test of newly\ud developed and existing methods for reference satellite determination using GPS data processing for baseline estimation. A set of observations from permanent stations that form three baselines with different lengths is chosen in order to test and analyze the effect of individual methods on different baselines. Furthermore, we test how limiting of reference satellite duration and using different altitude limits for reference satellite affect the results of GPS data processing. A comparison is made between developed and existing method, both using different altitude limits for reference satellite. We finish with analysis of results and final conclusions

Atipični aktinomikotični piogranulom frontalne i parijetalne regije u srne (Capreolus capreolus) - prikaz slučaja

Actinomycosis is a rare infectious bacterial disease that affects domestic and wild ruminants, horses, small carnivores, monkeys, rabbits, birds and humans. Actinomyces spp. are gram-positive, acid-fast-negative filamentous bacteria which can grow anaerobically and cause abscesses and pyogranulomatous inflammation. In this report, a case of an atypical actinomycotic pyogranuloma due to Actinomyces sp. of the frontal and parietal region of the head in a roe deer (Capreolus capreolus) is described. Based on the gross and histopathological findings and bacterial culture results, a diagnosis of extrafacial actinomycosis affecting the neurocranial part of the skull and soft tissues of the frontal and parietal regions was made.Aktinomikoza je rijetka zarazna bakterijska bolest koja zahvaća domaće i divlje preživače, konje, male mesojede, majmune, kuniće, ptice i ljude. Bakterije Actinomyces spp. jesu gram-pozitivne, filamentne bakterije koje se boje Ziehl-Neelsenovim bojenjem, a mogu rasti anaerobno te uzrokovati apscese i piogranulomatoznu upalu. U ovom se radu opisuje slučaj atipičnog aktinomikotičnog piogranuloma uzrokovanog bakterijom Actinomyces sp. u frontalnoj i parijetalnoj regiji glave srne (Capreolus capreolus). Na temelju makroskopskog i histopatološkog nalaza te bakteriološke pretrage ustanovljena je dijagnoza ekstrafacijalne aktinomikoze koja je zahvatila neurokranijalni dio lubanje i meka tkiva frontalne i parijetalne regije

Epidemiology of Malignant Pleural Mesotheliomas in Croatia in the Period from 1989 to 1998

Malignant pleural mesotheliomas are rare tumors. Their occurrence is often associated with the exposure to asbestos. Asbestos is widely used in various industries as well as for many types of products in everyday use. In Croatia in the period from 1989 to 1998, the rate of incidence was 0.4–1.1 / 100,000. The highest rate of incidence was in the Districts of Istria (2.9) and Split-Dalmatia (2.5). It is more frequent among males than among females with a ratio of 3.2:1. It rarely occurs before the age of 40 and most of the patients suffering from the disease are more than 65 years old. About 12% of mesotheliomas metastasize into regional lymph nodes and 17% of them into distant organs. The disease unavoidably leads to death and, according to the data obtained in Croatia in the period from 1989 to 1998 the mortality and incidence are very close

Lung Lavage Neutrophils, Neutrophil Elastase and Albumin in the Prognosis of Pulmonary Sarcoidosis

The authors measured the bronchoalveolar lavage fluid (BALF) neutrophils, neutrophil elastase and albumin in 60 patients with pulmonary sarcoidosis, 18 patients with other interstitial lung diseases and 14 healthy controls in order to evaluate its significance in the prognosis of sarcoidosis. The concentrations were measured by enzymoimmunoassay and radial immunodiffusion (LC plates). Obtained values were correlated with some clinical indices, radiological stage and lung function values. The patients were followed up for 22.3 6.8 months. At the end of observation period the outcome of sarcoidosis has been evaluated upon the findings of chest radiograms and lung function tests. The length of duration of the disease correlated with the lung lavage neutrophil counts (r = 0.2535; p < 0.05). Significantly higher values of BALF elastase were obtained in III radiologic stage than II and I. Patients with high BALF albumin had more often dispnoa (p < 0.05) and chronic forms of the disease (p < 0.05). The values were high in patients in II and III radiologic stage. Unfavorable outcome of chest radiograms was announced by high BALF albumins (p < 0.05). The measurement of BALF neutrophils, neutrophil elastase and albumin are helpful in clinical management and estimation of the prognosis in patients with pulmonary sarcoidosis

Population-based consultation patterns in patients with shoulder pain diagnoses

Background: To assess the annual consultation prevalence and new onset consultation rate for doctor-diagnosed shoulder pain conditions. Methods: We identified all residents in the southernmost county in Sweden who received a shoulder pain diagnosis during 2006 (ICD-10 code M75). In subjects who did not consult due to such disorders during 2004 and 2005, we estimated the new onset consultation rate. The distribution of specific shoulder conditions and the length of the period of repeated consultation were calculated. Results: Annual consultation prevalence was 103/10 000 women and 98/10 000 men. New onset consultation rate was 80/10 000 women (peak in age 50-59 at 129/10 000) and 74/10 000 men (peak in age 60-69 at 116/10 000). About one fifth of both genders continued to consult more than three months after initial presentation, but only a few percent beyond two years. Rotator cuff - and impingement syndromes were the most frequent diagnoses. Conclusion: The annual consultation prevalence for shoulder pain conditions (1%) was similar in women and men, and about two thirds of patients consulted a doctor only once. Impingement and rotator cuff syndromes were the most frequent diagnoses

Korelacija scintigrafije pluća Ga-67 s RTG pluća i testovima plućne funkcije u oboljelih od sarkoidoze

In order to assess the usefulness of Ga-67 scintigraphy in the evaluation of sarcoidosis activity, 44 patients including 14, 20 and 10 patients with radiologic stage I, II and III, respectively, were examined. Control group consisted of 22 subjects with healthy lungs who underwent Ga-67 scintigraphy for extrathoracic disease. An objective method of quantitative computer analysis was used on scintigram interpretation. Results were expressed as mean impulse count per pixel of the given area in the left and right hilar region, left and right lung, and in the area of focal accumulation if present. In sarcoidosis patients, the mean impulse count was statistically significantly higher in all regions than in the control group (p<0.0001 for left hilum, right hilum and right lung; and p<0.001 for left lung). The mean impulse count showed correlation with pathologic finding. Pathologic accumulation of Ga-67 in the hilar region was evident in 37 (84.1%) patients, and in the region of pulmonary parenchyma in 31 (70.5%) patients, and showed statistically significant correlation with radiologic staging of sarcoidosis (p<0.01). However, scintigraphy supplemented radiologic staging by providing additional information on the disease extent. In 35.7% of patients with X-ray stage I sarcoidosis, scintigraphy revealed pathologic accumulation of Ga-67 also in pulmonary parenchyma, whereas in as many as 70% of patients with X-ray stage III sarcoidosis the pathologic accumulation of Ga-67pointed to the disease activity in the lymph nodes of the hilum. Only three (6.7%) patients were free from any form of pathologic Ga-67 accumulation. The patients with pathologic Ga-67 accumulation in the lung parenchyma (n=31) had a more severe form of the disease with lower values of pulmonary function tests, i.e. forced vital capacity (FVC), forced expiratory volume in first second (FEV 1), diffusion capacity for carbon monoxide (DLCO) and arterial blood partial oxygen pressure (pO 2). Forced vital capacity as an indicator of ventilation restrictive impairments was statistically significantly lower in the group of patients with pathologic accumulation of Ga-67 in pulmonary parenchyma as compared with the group of patients without it (p<0.01). The decrease in diffusion capacity correlated statistically significantly with the increase in the pathologic accumulation of Ga-67 in pulmonary parenchyma (p<0.01). Thus, lung Ga-67scintigraphy was found to be a highly sensitive marker of the extent and activity of sarcoidosis, however, due to the low specificity of the method its use in good clinical practice should be reserved for diagnostically and therapeutically vague cases, with due consideration of the irradiation dose and cost.Radi procjene značenja scintigrafije pluća s Ga-67 u oboljelih od sarkoidoze ispitana su 44 bolesnika, i to 14 u I., 20 u II. i 10 u III. radiološkom stadiju bolesti. Kontrolnu skupinu činile su 22 osobe sa zdravim plućima u kojih je scintigrafija s Ga-67 rađena zbog ekstratorakalne bolesti. Pri tumačenju scintigrama rabljena je objektivna metoda kvantitativne kompjutorske analize gdje se rezultat izražava kao prosječan broj impulsa po kvadrantu zadane regije u području lijevog i desnog hilusa, lijevog i desnog pluća, te u području žarišnog nakupljanja ako je ono izraženo. U oboljelih od sarkoidoze prosječan broj impulsa za svaku regiju bio je statistički značajno viši od onoga u kontrolnoj skupini (p<0,0001 za lijevi hilus, desni hilus i desno pluće, te p<0,001 za lijevo pluće). Prosječan broj impulsa pratio je radiološki nalaz. Patološko nakupljanje Ga-67 u području hilusa bilo je očito u 37(84,1%) bolesnika, a u području plućnog parenhima u 31 (70,5%) bolesnika, uza statistički značajnu korelaciju s radiološkim stadijem sarkoidoze (p<0,01). Međutim, scintigrafija je dopunila radiološko određivanje stadija bolesti pruživši dodatne informacije o proširenosti bolesti. Tako je kod 35,7% bolesnika u I. rtg stadiju bolesti patološko nakupljanje Ga-67 bilo očito i u plućnom parenhimu, dok je u čak 70% bolesnika s III. rtg stadijem patološko nakupljanje Ga-67 upućivalo na aktivnost procesa i u limfnim čvorovima hilusa. Samo troje (6,7%) bolesnika nije imalo patološko nakupljanje Ga-67 u bilo kojem obliku. Bolesnici s patološkim nakupljanjem Ga-67 u plućnom parenhimu (n=31) imali su teži oblik bolesti s nižim vrijednostima testova plućnih funkcija, tj. forsiranog vitalnog kapaciteta, forsiranog ekspiracijskog volumena u prvoj sekundi, difuzijskog kapaciteta za ugljični monoksid i parcijalnog tlaka kisika u arterijskoj krvi. Forsirani vitalni kapacitet kao pokazatelj restriktivnih smetnja ventilacije bio je statistički značajno niži u skupini bolesnika s patološkim nakupljanjem Ga-67 u plućnom parenhimu u usporedbi sa skupinom bez patološkog nakupljanja (p<0,01). Pad difuzijskog kapaciteta je statistički značajno korelirao s porastom patološkog nakupljanja Ga-67 u plućnom parenhimu (p<0,01). Dakle, scintigrafija pluća s Ga-67 vrlo je osjetljiv biljeg proširenosti i aktivnosti kod sarkoidoze, međutim, ima nisku specifičnost, pa ovu metodu u dobroj kliničkoj praksi treba rabiti u dijagnostički i terapijski dvojbenim slučajevima, vodeći pritom računa o dozi ozračivanja i cijeni