Structure and Bonding in Some Platinum Complexes

In this thesis the technique of X-ray crystal structure analysis is applied to the study of molecular structure, conformation and bonding in some platinum(ll) and platinum(I) complexes. The contents are divided into three parts. In Part I some of the theoretical and practical aspects of the X-ray diffraction methods, pertinent to the work described in Parts II and III, are surveyed. Part II, which is presented in six Chapters, is concerned with the structures of eight square-planar platinum(ll) complexes. Current views on trans- and cis-influence of ligands and some aspects of metal-phosphorus bonding are first reviewed (Chapter 1). This is followed by a description of the crystal structure analyses of three platinum(II) complexes containing the novel ligand PMe2C6F5 (Chapter 2). The interest is centred on the effect of electron-withdrawal of phosphine substituents on the metal-ligand bonding. Chapter 3 is devoted to the structure analyses of the complexes cis-PtCl2(PEt3)L, where L=PEt3 and CO. This work completes a systematic study of such complexes and the results are discussed in terms of the cis and trans-influence of the ligands. The constancy of the observed triethyl-phosphine conformation in square-planar platinum complexes has led to molecular mechanics calculations on the triethylphosphine molecule, which are also described. In Chapter 4 the structure of a platinum(II) complex which provides the first known example of a metallated phosphine-carborane is described. The interest in the effect of strongly electron-withdrawing substituents on sulphur- donor atom on metal-ligand bonding has led to determination of the crystal structure of cis-PtCl2(CF3SCH2CHMeSCF3), presented in Chapter 5. Chapter 6 is devoted to the structure analysis of trans-[PtCl(COEt)(PMe2Ph)2 . This complex displays an unusually large 1J(Pt-P) coupling constant. The X-ray study was carried out in order to examine the correlation between Pt-P bond lengths and coupling constants in bridged binuclear platinum(II) species. Part III is concerned with the structure analyses of two closely similar and novel platinum(l) complexes, which contain direct metal-ligand bonds

Upravljanje ljudskim potencijalima u funkciji učinkovitosti policijske organizacije – percepcija policijskih rukovoditelja

Upravljanje ljudskim potencijalima u funkciji učinkovitosti policijske organizacije – percepcija policijskih rukovoditelj

Raman Spectroscopic Signature of Ectoine Conformations in Bulk Solution and Crystalline State

Recent crystallographic results revealed conformational changes of zwitterionic ectoine upon hydration. By means of confocal Raman spectroscopy and density functional theory calculations, we present a detailed study of this transformation process as part of a Fermi resonance analysis. The corresponding findings highlight that all resonant couplings are lifted upon exposure to water vapor as a consequence of molecular binding processes. The importance of the involved molecular groups for water binding and conformational changes upon hydration is discussed. Our approach further shows that the underlying rapid process can be reversed by carbon dioxide saturated atmospheres. For the first time, we also confirm that the conformational state of ectoine in aqueous bulk solution coincides with crystalline ectoine in its dihydrate state, thereby highlighting the important role of a few bound water molecules

Vertical Electrical Sounding (VES) investigation for road failure along Mekelle – Abi-Adi road segment, northern Ethiopia

Roads constructed along the mountainous terrains of Ethiopia are susceptible to landslides mostly during rainy season. Mekelle – Abi Adi road is one of the economically important road corridors that connects many towns with Mekelle city. However, the asphalt road segment is heavily affected by quasi-translational type of landslide which hinders traffic flow of the area. Vertical electrical sounding (VES) method was applied to investigate subsurface geology of the road failure along Mekelle – Abi-Adi asphalt road, northern Ethiopia. The geo-electric section result revealed that the shallow subsurface geology of the site is characterized by four distinct geological formations, from top to bottom are: shale, shale-limestone intercalation, limestone and shale-gypsum units. The subgrade of the failed road section is shale unit which is overlain by jointed sandstone unit. The sandstone unit serves as a recharge zone to the bottom shale layer by percolating water via sub-base fill materials which in turn blocks vertical percolation and promote seepage force to the overlying soil mass. Hence, the road failure in the study area seems to be caused due to the development of pore water pressure in the shale layer which soaked water during heavy rainfall. The recommended remedial method for the road failure is re-designing of the affected route from chainage 48 km+850 m to 49 km+250 m towards the northwest of the study area and excavates the top 6 m shale unit

Koncentracije ostataka veterinarskih lijekova u mlijeku s individualnih farmi u Hrvatskoj

A total of 119 raw milk samples collected at individual small milk-producing facilities and collection tanks of milk routes from five counties of east and north continental Croatia were examined for chloramphenicol, sulfonamides, tetracyclines, gentamicin, streptomycin, dihydrostreptomycin, flumequine and enrofloxacin from January to March of 2011. Immunoassay methods used for drug determination were validated according to the guidelines laid down by European Commission Decision 2002/657/EC. Data indicated that the methods are appropriate for the detection of antibiotics measured. Measured mean values (μg L-1) of antibiotics were: 0.005 for chloramphenicol, 3.67 for sulfonamides, 2.83 for tetracyclines, 1.10 for gentamicin, 2.64 for streptomycin, 7.67 for dihydrostreptomycin, 10.4 for flumequine and 4.11 for enrofloxacin. None of samples analyzed showed the presence of veterinary drug residues above the maximum residues levels (MRLs) established by European Union and Croatian legislation. The calculated estimated daily intakes (EDIs) for the average daily milk consumption of 300 mL for an adult in Croatia for examined antibiotics showed levels 20 to 1640 times lower than the values of acceptable daily intakes (ADIs) fixed by European Medicines Agency and World Health Organization. This suggested that toxicological risk associated with the consumption of analysed milk could not be considered a public health issue with regards to these veterinary drugs.Tijekom 3 mjeseca analizirano je ukupno 119 uzoraka mlijeka na veterinarske lijekove: kloramfenikol, sulfonamide, tetraciklin, gentamicin, streptomicin, dihidrostreptomicin, flumekin i enrofloksacin. Imunoenzimske metode korištene za određivanje veterinarskih lijekova validirane su prema odredbama propisanim Odlukom Europske komisije 2002/657/ EC. Rezultati validacije metoda pokazuju da su primijenjene metode prikladne za tu namjenu. Ni u jednom uzorku mlijeka nije utvrđena koncentracija ostataka veterinarskih lijekova iznad najviših dopuštenih količina (NDK) utvrđenih Europskom legislativom. Izračunate procjene unosa određivanih lijekova mlijekom su za 20 do 1640 puta niže od zadanih prihvatljivih dnevnih količina unosa. Prema dobivenim rezultatima može se zaključiti da određivani veterinarski lijekovi ne predstavljaju toksikološki rizik za potrošače s obzirom na rezultate analize mlijeka na ostatke antibiotika s malih farmi

Koncentracije ostataka veterinarskih lijekova u mlijeku s individualnih farmi u Hrvatskoj

A total of 119 raw milk samples collected at individual small milk-producing facilities and collection tanks of milk routes from five counties of east and north continental Croatia were examined for chloramphenicol, sulfonamides, tetracyclines, gentamicin, streptomycin, dihydrostreptomycin, flumequine and enrofloxacin from January to March of 2011. Immunoassay methods used for drug determination were validated according to the guidelines laid down by European Commission Decision 2002/657/EC. Data indicated that the methods are appropriate for the detection of antibiotics measured. Measured mean values (μg L-1) of antibiotics were: 0.005 for chloramphenicol, 3.67 for sulfonamides, 2.83 for tetracyclines, 1.10 for gentamicin, 2.64 for streptomycin, 7.67 for dihydrostreptomycin, 10.4 for flumequine and 4.11 for enrofloxacin. None of samples analyzed showed the presence of veterinary drug residues above the maximum residues levels (MRLs) established by European Union and Croatian legislation. The calculated estimated daily intakes (EDIs) for the average daily milk consumption of 300 mL for an adult in Croatia for examined antibiotics showed levels 20 to 1640 times lower than the values of acceptable daily intakes (ADIs) fixed by European Medicines Agency and World Health Organization. This suggested that toxicological risk associated with the consumption of analysed milk could not be considered a public health issue with regards to these veterinary drugs.Tijekom 3 mjeseca analizirano je ukupno 119 uzoraka mlijeka na veterinarske lijekove: kloramfenikol, sulfonamide, tetraciklin, gentamicin, streptomicin, dihidrostreptomicin, flumekin i enrofloksacin. Imunoenzimske metode korištene za određivanje veterinarskih lijekova validirane su prema odredbama propisanim Odlukom Europske komisije 2002/657/ EC. Rezultati validacije metoda pokazuju da su primijenjene metode prikladne za tu namjenu. Ni u jednom uzorku mlijeka nije utvrđena koncentracija ostataka veterinarskih lijekova iznad najviših dopuštenih količina (NDK) utvrđenih Europskom legislativom. Izračunate procjene unosa određivanih lijekova mlijekom su za 20 do 1640 puta niže od zadanih prihvatljivih dnevnih količina unosa. Prema dobivenim rezultatima može se zaključiti da određivani veterinarski lijekovi ne predstavljaju toksikološki rizik za potrošače s obzirom na rezultate analize mlijeka na ostatke antibiotika s malih farmi

Combined influence of ectoine and salt: spectroscopic and numerical evidence for compensating effects on aqueous solutions

Ectoine is an important osmolyte, which allows microorganisms to survive in extreme environmental salinity. The hygroscopic effects of ectoine in pure water can be explained by a strong water binding behavior whereas a study on the effects of ectoine in salty solution is yet missing. We provide Raman spectroscopic evidence that the influence of ectoine and NaCl are opposing and completely independent of each other. The effect can be explained by the formation of strongly hydrogen-bonded water molecules around ectoine which compensate the influence of the salt on the water dynamics. The mechanism is corroborated by first principles calculations and broadens our understanding of zwitterionic osmolytes in aqueous solution. Our findings allow us to provide a possible explanation for the relatively high osmolyte concentrations in halotolerant bacteria

Foundation of modern police sciences and its contribution to the police practice in the European union

Rasprava o znanstvenom utemeljenju policije kao institucije i kao funkcije (djelatnosti) u europskom prostoru razvija se tek sredinom XX. stoljeća. Izvorišno, nastaje kao znanost o vladanju ili upravljanju državom, potom se smatra pravnom i kriminološkom znanosti, a u novije doba se razvija u kontekstu socioloških disciplina. Kao dio kameralnih znanosti i upravljanja unutarnjom sigurnošću u Njemačkoj, poistovjećivanja sa znanosti o upravljanju državom u Francuskoj, u sklopu pravnih, političkih ili vojnih znanosti u drugim državama, do škotskog i britanskog koncepta prevencije i brige o uređenju civilnog društva, policijska znanost evoluira kao odraz shvaćanja uloge policije u društvu. Tendencije sužavanja policijske znanosti na proučavanje kriminaliteta i počinitelja ili puko provođenje zakona, odnosno uklapanje u kriminologiju ili kazneno pravo, zanemaruju istraživanja o policijskom djelovanju u kojem policijski službenik štiti građane i javna dobra, obavlja kriminalistička istraživanja ili primjenjuje druge policijske ovlasti. Jasnim određenjem prirode i svrhe policijske djelatnosti, što je determinira kao sigurnosnu znanost, te argumentiranjem posebnosti predmeta, metodologije i policijske znanstvene spoznaje, na tragu razvoja i rasprava o policijskim znanostima u državama Europske unije, ovim radom se aktualizira znanstvena perspektiva i pozicioniranje policijske znanosti u Europi i svijetu s posebnim osvrtom na Republiku Hrvatsku.Debates about the scientific foundation of the police as an institution-police and as a function-policing developed in the European context in the middle of 20th century. Originally, created as a science of governance, than considered as legal and criminological science, in more recent times police science develops only in the context of sociological disciplines. As part of cameral sciences and management of internal security in Germany, identifying with the science of governance in France, within the legal, political or military sciences in other countries, to the Scottish and British concept of prevention and concern about organizing of civil society, police science evolves as reflect of understanding the role of police in society. Tendencies narrowing police science to the study of crime and offenders or law enforcement, or integration into the Criminology and Criminal Law, neglects researches about police activity in which the police officer protects the citizens and the public properties and performs criminal investigations or applies other police powers. The clear determination of the nature and purpose of police activity, as defining it as security science, and argumentation of particularities of the object, the methodology and police scientific cognition, following the developments and discussions of police sciences in the European Union, this study actualizes the scientific perspective and positioning of police science in Europe, in World, with special review to the Republic of Croatia

Kontrola ostataka levamisola u mlijeku primjenom validirane metode tekućinske kromatografije-tandemske-spektrometrije masa

Concentrations of the anthelmintic agent levamisole were measured in a total of 85 raw cow milk samples collected during 2014 from dairy farms across Croatia. The liquid chromatographytandem mass spectrometry (LC-MS/MS) method used for levamisole quantification was validated according to the criteria set by Commission Decision 2002/657/EC. The following validation parameters were determined: limit of decision (CCα) 0.55 μg kg-1, detection of capability (CCβ) 0.59 μg kg-1, limit of detection (LOD) 0.06 μg kg-1, limit of quantification (LOQ) 0.22 μg kg-1, precision and accuracy (expressed as recovery) 97.3-100 %, intra-laboratory reproducibility (RSD) 4.2-5.6 %. Levamisole levels for 45 of the total of 85 samples were below the LOD value (0.06 µg kg-1). In the remaining 40 milk samples, levamisole was measured in the range from 0.061 to 0.142 µg kg-1 and the mean value was 0.092 µg kg-1. Accordingly, all concentrations analysed were below the LOQ value (0.22 µg kg-1) and limit of decision (CCα) of the method used.Koncentracije anthelmintika levamisola određene su u ukupno 85 uzoraka sirovog kravljeg mlijeka prikupljenih tijekom 2014. na mliječnim farmama iz cijele Hrvatske. Za kvantifikaciju levamisola korištena je metoda tekućinske kromatografije-tandemske- spektrometrije masa (LC-MS/MS) koja je validirana u skladu s kriterijima utvrđenim Odlukom Komisije 2002/657/EZ. Utvrđeni su sljedeći parametri validacije: granična koncentracija određivanja (CCα) 0,55 ug kg-1, sposobnost dokazivanja (CCβ) 0,59 ug kg-1, granica određivanja (LOD) 0,06 ug kg-1, granica kvantifikacije (LOQ) 0,22 ug kg-1, preciznost i točnost (izraženi kao iskorištenje) 97,3- 100,0 %, unutarlaboratorijska obnovljivost (RSD) 4,2- 5,6 %. Koncentracije levamisola za 45 od ukupno 85 uzoraka bile su ispod vrijednosti LOD (0,06 ug kg-1). U preostalih 40 uzoraka mlijeka, levamisol je izmjeren u rasponu od 0,061 do 0,142 ug kg-1, a srednja vrijednost je bila 0,092 ug kg-1. Zaključno, sve koncentracije analizirane su ispod LOQ vrijednosti (0,22 ug kg-1) i CCα, granične koncentracije metode

Crime in the COVID-19 Pandemic Atmosphere in Croatia

Ovo istraživanje obuhvaća analizu ukupnog kriminaliteta s detaljnim uvidom u opći ili konvencionalni kriminalitet u petogodišnjem razdoblju prije nastupanja pandemije bolesti COVID-19 (2015. – 2019.) u odnosu na godinu pandemije (2020.). Empirijska analiza temelji se na sekundarnim podacima registriranih kaznenih djela i prekršaja, za tu svrhu zatraženim i dobivenim od Ministarstva unutarnjih poslova Republike Hrvatske, što predstavlja posredno mjerenje kriminaliteta na određenom području (Palmer, 2020.). Problem eksplorativnog istraživanja u ovom radu stjecanje je novih spoznaja o eventualnim promjenama u opsegu, strukturi i dinamici kriminaliteta te tipologiji i obrascima policijski registriranih kaznenih djela i prekršaja u pandemijskom kriznom razdoblju, a u odnosu na prethodno petogodišnje razdoblje u Hrvatskoj. Dobiveni rezultati promatraju se kroz primjenjivost teorijskih koncepata ekološke kriminologije u objašnjenju promjene trendova u tipologiji i obrascima kriminalnog i devijantnog ponašanja. Smisao istraživanja bio je prikazati kako novonastala pandemijska svakodnevica utječe općenito na pokretljivost ukupnog kriminaliteta, ali i na specifične segmente kriminaliteta na području Republike Hrvatske i pojedinih policijskih uprava.This research includes an analysis of total crime with a detailed insight into common or conventional crime in the five-year period before the onset of the COVID-19 pandemic (2015- 2019) compared to the year of the COVID-19 pandemic (2020). Empirical analysis is based on secondary data of registered crimes and misdemeanors for this purpose requested and obtained from the Croatian Ministry of Interior, which is an indirect measurement of crime in a particular area (Palmer, 2020). The problem of exploratory research in this paper is the acquisition of new cognition about possible changes in the scope, structure and dynamics of crime and the typology and patterns of police registered crimes and offences in the pandemic crisis period, compared to the previous five years in Croatia. The obtained results are observed through the applicability of theoretical concepts of environmental criminology in explaining the change of trends in typology and patterns of criminal and deviant behavior. The purpose of the research was to show how the emerging pandemic influences everyday life and affects the mobility of overall crime in general, but also the specific segments of crime in the Republic of Croatia and individual police directorates