Hydrogen bonding and proton transfer in binary solids of N-(2-carboxyphenyl)glycerine and pyridine derivatives

Za potrebe ovoga rada pripravljen je N-(2-karboksifenil)glicin – dikiselina s karboksil-nim skupinama na aromatskom i alifatskom dijelu molekule, a kristalizacijom iz otopine pri-pravljeni su kristali binarnih krutina dikiseline s petnaest piridinskih derivata. Dobivene su kru-tine strukturno i termički okarakterizirane difrakcijom rentgenskog zračenja na jediničnom kri-stalu, difrakcijom rentgenskog zračenja na praškastom uzorku, razlikovnom pretražnom kalo-rimetrijom i termogravimetrijskom analizom. U jedanaest krutina uočeno je preferencijalno po-vezivanje piridina i alifatske karboksilne skupine. Analizom geometrija vodikovih veza te izra-čunatih naboja i elektrostatskih potencijala pronađeno je da je alifatska karboksilna skupina bolji donor vodikove veze od aromatske. Sve duljine vodikovih veza u kojima sudjeluje alifat-ska karboksilna skupina uglavnom slijede empirijsko pravilo temeljeno na razlici vrijednosti pKa odgovarajućih piridinskih derivata i karboksilne skupine. Prijenos protona s karboksilne kiseline na piridinski dušik uočen je u jedanaest struktura (pri čemu su nastale soli), dok su preostale četiri krutine kokristali. Uočeno je da prijenos protona ima bitan utjecaj na pakiranje u kristalu: u kokristalima molekule su povezane u diskretne molekulske komplekse, dok su u solima pronađeni lanci monoaniona kao glavni motiv povezivanja.Within this master thesis, N-(2-carboxyphenyl)glycine − a carboxylic acid with carboxyl groups on aromatic and aliphatic part of the molecule has been synthesized. Its binary solids single crystals with fifteen pyridine derivatives have been prepared by crystalization from so-lution. Obtained compounds were structuraly and thermally characterized by single crystal and powder X-ray diffraction, differential scanning calorimetry and thermogravimetric analysis. In eleven obtained compounds preferentially binding of pyridine nitrogen and aliphatic carboxyl group has observed and it was found that this carboxyl group is a better hydrogen bond donor than aromatic carboxyl group, what is explained by hydrogen bond geometries and calculated NBO charges and electrostatic potentials of carboxyl hydrogen atoms. All noticed hydrogen bond lenghts on aliphatic carboxyl group follows empirical „pKa rule”. Proton transfer from carboxyl group to pyridine nitrogen was observed in eleven compounds leading to formation of salts, while the remaining four are co-crystals. It was also observed that the proton transfer has considerable effect on the crystal packing: in co-crystals molecules are linked into a discrete molecular complexes, while in salts chains of monoanions are observed as the main packing motif

Tautomeric Equilibrium of an Asymmetric β-Diketone in Halogen-Bonded Cocrystals with Perfluorinated Iodobenzenes

In order to study the effect of halogen bond on tautomerism in β-diketones in the solid-state, we have prepared a series of cocrystals derived from an asymmetric β-diketone, benzoyl-4-pyridoylmethane (b4pm), as halogen bond acceptor and perfluorinated iodobenzenes: iodopentaflourobenzene (ipfb), 1, 2-, 1, 3- and 1, 4-diiodotetraflorobenzene (12tfib, 13tfib and 14tfib) and 1, 3, 5-triiodo-2, 4, 6-trifluorobenzene (135titfb). All five cocrystals are assembled by I···N halogen bonds involving pyridyl nitrogen and iodoperfluorobenzene iodine resulting in 1:1 (four compounds) or 1:2 (one compound) cocrystal stoichiometry. Tautomer of b4pm in which hydrogen atom is adjacent to the pyridyl fragment was found to be more stable in vacuo than tautomer with a benzoyl hydroxyl group. This tautomer is also found to be dominant in the majority of crystal structures, somewhat more abundantly in crystal structures of cocrystals in which additional I···O halogen bond with the benzoyl oxygen has been established. Attempts have also been made to prepare an equivalent series of cocrystals using a closely related asymmetric β-diketone, benzoyl-3-pyridoylmethane (b3pm) ; however, all attempts were unsuccessful, which is attributed to more effective crystal packing of b3pm isomer compared to b4pm, which reduced the probability of cocrystal formation

Hranidbena vrijednost termički dorađenog bijelog i crnog kruha u hranidbi brojlera

Growing consumer demand for safe and affordable food as well as the need for a sustainable food supply will force the producers to explore methods for production output increasing. The poultry industry has an important role in the provision of a sustainable food supply, especially because chickens have a high feed conversion efficiency compared to other birds or livestock and, chicken meat is a low greenhouse gas emission food compared to other sources of dietary protein and has accessible source of protein with a low-fat content. The most important aspect of broiler production is feeding, and it represents about 70% of total costs. In order to facilitate the broilers, feed mixture production, it is tending to replace corn component, with a new, cheaper but high-quality component. As an alternative, it is possible to use the old bread, which would enable its remediation. Its use in broiler feeding is possible only after thermal treatment. Following this work will include the possibilities of using 5 and 10% of the old white and brown bread share in broilers feed mixture after thermal processing by extrusion. Feeding with both types of old extruded bread proved to be satisfying and did not affect broilers performance so generally dried bread can be used in chicken feed by as a partial replacement for maize component. Although both breads have proved good feeding quality, slightly better results were obtained in feeding with 10% share of brown bread.Rastuća potražnja potrošača za sigurnom i pristupačnom hranom, kao i potreba za održivom opskrbom hranom prisilit će proizvođače da istraže načine povećanja proizvodnje. Peradarska industrija ima važnu ulogu u osiguravanju održive opskrbe hranom, posebno zato što pilići imaju visoku učinkovitost konverzije hrane u odnosu na druge ptice ili stoku, a pileće meso je hrana niske emisije stakleničkih plinova u usporedbi s drugim izvorima prehrambenih proteina i ima pristupačan izvor proteina s niskim udjelom masti Najvažniji aspekt proizvodnje brojlera je hranidba, koja predstavlja oko 70% ukupnih troškova. Kako bi se olakšala proizvodnja krmnih smjesa za piliće, teži se zamjeni komponentu kukuruza novom, jeftinijom ali kvalitetnijom komponentom. Kao zamjensku komponentu, moguće je koristiti stari kruh čime bi se istovremeno omogućila njegova sanacija. Njegova uporaba u hranidbi brojlera moguća je samo nakon termičke dorade. Temeljem navedenog, ovaj rada obuhvaća mogućnosti korištenja 5 i 10% udjela starog bijelog i crnog kruha, u krmnoj smjesi za brojlere, nakon termičke dorade ekstruzijom. Hranidba s oba tipa starog ekstrudiranog kruha pokazala se zadovoljavajućom i nije utjecala na prirast brojlera pa se općenito, sušeni kruh može koristiti u hranidbi pilića kao djelomična zamjena za kukuruznu komponentu. Iako su se obje vrste kruha pokazale kvalitetne prilikom hranjenja, nešto bolji rezultati dobiveni su u hranidbi s 10% udjela starog crnog kruha

NUTRITIVNA ISKORISTIVOST STAROGA CRNOG KRUHA U HRANIDBI PILIĆA

The most important aspect of broiler production is feeding, whose costs represent about 70% of total costs. Thus, the growth of poultry production has been based on a strong consumer demand for products that are cheap, safe, and healthy. That kind of product is old bread, whose return from the store represent a problem for its remediation. For the use of the old bread as a feed, the European Union has promulgated a series of regulations and directives, which order a ban on its utilization without prior treatment. The most common treatments are pelleting and extrusion. In poultry, the upper limit for the use of the old bread in feedstuff is often prescribed and amounts to 15%. The aim of this paper was to determine a possibility to use 5 and 10% old brown pelleted bread in feed mixtures for broilers fattening. The study has shown that the addition of old bread significantly improves broiler production indicators. The best results and a more favorable ratio of omega 6 and omega 3 fatty acids in the chicken muscles were obtained in the group fed with a 10‐percent share of old brown bread (p<0.05). Such a processed old bread can be used as a new ingredient in animal feed production as a partial replacement for maize component.Najvažniji aspekt proizvodnje brojlera jest hranidba, čiji troškovi čine oko 70% ukupnih troškova proizvodnje. Tako se rast peradarske proizvodnje temelji na snažnoj potražnji potrošača za proizvodima koji su jeftini, sigurni i zdravi. Takav je proizvod stari kruh, čije vraćanje iz trgovine predstavlja problem sanacije. Za korištenje staroga kruha kao hrane za životinje Europska unija donijela je niz propisa i smjernica kojima se propisuje zabrana korištenja bez prethodne dorade. Najčešći tretmani su peletiranje i ekstruzija. Kod peradi je često propisana gornja granica za uporabu staroga kruha u hrani za životinje, a ona iznosi 15%. Cilj ovoga rada bio je utvrditi mogućnost korištenja 5 i 10% staroga crnog peletiranog kruha u krmnim smjesama za tov brojlera. Istraživanje je pokazalo da dodavanje staroga kruha značajno poboljšava proizvodne pokazatelje brojlera. Najbolji rezultati i povoljniji omjer omega 6 i omega 3 masnih kiselina u pilećem mišiću dobiveni su u skupini koja se hranila s 10% udjela staroga crnog kruha (p<0,05). Takav obrađeni stari kruh može se koristiti kao novi sastojak u proizvodnji hrane za životinje kao djelomična zamjena za kukuruznu komponentu

RAPE SEED OIL-CAKE IN LAYERS NUTRITION

Pogača uljane repice, kao glavni sporedni proizvod pri proizvodnji ulja godinama predstavlja veliki izazov istraživačima i nutricionistima glede njene uporabe u hranidbi kokoši nesilica. Cilj ovog istraživanja bio je utvrditi utjecaj 8 i 16 % pogače uljane repice domaćeg kultivara Bristol u krmnim smjesama na proizvodna svojstva kokoši nesilica. U pokusu je korišteno 90 kokoši Hrvatica u razdoblju od 24. do 32. tjedna nesivosti. Kokoši su bile raspoređene u 30 kaveza po tri kokoši u svakom. Hranidba kokoši s 8 % (PN-8) i 16 % (PN-16) pogače uljane repice u hrani nije imala (p>0.05) negativan utjecaj na prosječnu masu jaja te prosječnu nesivost kokoši. Kod skupine PN-16 zabilježen je najviši mortalitet (10 %), što je značajno (p0.05). Prosječne ocjene za miris, okus, boju i opću ocjenu jaja u skupini PN-16 bile su niže u odnosu na ostale tretmane. Iz svega gore navedenoga vidljivo je da se pogače uljane repice dobivene iz sjemena uljane repice domaćih kultivara Bristol može preporučiti u udjelu od 8 % u krmnim smjesama za kokoši nesilice.Rape seed oil-cake, as the main by-product in the production of oil has represented a great challenge to all researches and nutritionists for years related to its use in the feeding process of laying hens. The main goal of this research was to establish the influence of 8 % (PN-8) and 16 % (PN-16) rape seed oil-cake of domestic cultivar Bristol in feed mixture on the production quality of laying hens. While conducting the experiment, 90 Croatian hens were used, in the period of 24 to 32 weeks of egg production. Hens were sorted out in to 30 cages, 3 of them in each cage. The diet of respective hens with 8 and 16 % rape seed oil-cake had no negative (p>0.05) influence on the average egg mass and average egg production. The highest mortality (10%) was recorded in hens in group PN-16, which contributing significantly (p<0.05) to the lower total number of laid eggs during the experiment. In group PN-16 the highest consumption of feed mixture per kilo of egg mass and on average per one egg was recorded. The eggs of group PN-16 had a slightly higher value with respect to shell hardness, height of albumen, colour of egg yolk, and Haugh unit. Still, respective differences were not significant (p>0.05). Average marks for smell, taste, colour and general of eggs in the group of hens fed rape seed oil-cake of 16 % were lower compared to other treatments. Taking into consideration the above mentioned, it can be concluded that rape seed oil-cake of domestic cultivar Bristol can be recommended to be used in the portion of 8 % in feed mixture for laying hens

Cocrystallization of perfluoroiodobenzenes with simple pyridine derivatives – comparative evaluation of classical halogen bond donors

U sklopu disertacije pripravljeno je 37 novih kokristala jodperfluorbenzenâ i jednostavnih derivata piridina koji su strukturno i termički okarakterizirani. Po prvi puta su sustavno ispitana i uspoređena donorska svojstva komercijalnih jodperfluorbenzenâ i uočene su sličnosti i razlike u strukturama njihovih kokristala s jednostavnim derivatima piridina. Potvrđena je teza o 1,4-dijodtetrafluorbenzenu kao provjerenom i pouzdanom donoru halogenske veze koji tvori kokristale s 13 korištenih akceptora, dok je s 1,2-dijodtetrafluorbenzenom pripravljeno samo 5 kokristala. Ispitan je međuodnos geometrije molekula donora, iznosa elektrostatskih potencijala na donorskim atomima i prostornih ograničenja na nastajanje kokristala te njihov utjecaj na konačnu stehiometriju produkta. Također, bazičnost molekulâ akceptora istaknula se kao iznimno bitan faktor za pripravu kokristala s nešto slabijim donorima te kokristala s tritopičnim donorom halogenske veze, u kojemu su na molekulu donora vezane tri molekule akceptora.In this study, 37 novel cocrystals of iodoperfluorobenzenes and simple pyridine derivatives were prepared and structurally and thermally characterized. For the first time, donor properties of commercial iodoperfluorobenzenes were systematically examined and compared, and similarities and differences in their cocrystal structures with simple pyridine derivatives were observed. 1,4-diiodotetrafluorobenzene was proven as a reliable halogen bond donor with a total of 13 prepared cocrystals, while 1,2-diiodotetrafluorobenzene forms cocrystals with only 5 used acceptors. The relationship between the geometry of donor molecules, electrostatic potentials at the donor atoms and the steric effects on the formation of cocrystals was investigated as well as their influence on the final product stoichiometry. Additionally, the basicity of acceptor molecules has emerged as a highly important factor for the preparation of cocrystals with slightly weaker donors and for the synthesis of cocrystals with a tritopic halogen bond donor, in which three acceptor molecules are attached to the donor molecule

Cocrystallization of perfluoroiodobenzenes with simple pyridine derivatives – comparative evaluation of classical halogen bond donors

U sklopu disertacije pripravljeno je 37 novih kokristala jodperfluorbenzenâ i jednostavnih derivata piridina koji su strukturno i termički okarakterizirani. Po prvi puta su sustavno ispitana i uspoređena donorska svojstva komercijalnih jodperfluorbenzenâ i uočene su sličnosti i razlike u strukturama njihovih kokristala s jednostavnim derivatima piridina. Potvrđena je teza o 1,4-dijodtetrafluorbenzenu kao provjerenom i pouzdanom donoru halogenske veze koji tvori kokristale s 13 korištenih akceptora, dok je s 1,2-dijodtetrafluorbenzenom pripravljeno samo 5 kokristala. Ispitan je međuodnos geometrije molekula donora, iznosa elektrostatskih potencijala na donorskim atomima i prostornih ograničenja na nastajanje kokristala te njihov utjecaj na konačnu stehiometriju produkta. Također, bazičnost molekulâ akceptora istaknula se kao iznimno bitan faktor za pripravu kokristala s nešto slabijim donorima te kokristala s tritopičnim donorom halogenske veze, u kojemu su na molekulu donora vezane tri molekule akceptora.In this study, 37 novel cocrystals of iodoperfluorobenzenes and simple pyridine derivatives were prepared and structurally and thermally characterized. For the first time, donor properties of commercial iodoperfluorobenzenes were systematically examined and compared, and similarities and differences in their cocrystal structures with simple pyridine derivatives were observed. 1,4-diiodotetrafluorobenzene was proven as a reliable halogen bond donor with a total of 13 prepared cocrystals, while 1,2-diiodotetrafluorobenzene forms cocrystals with only 5 used acceptors. The relationship between the geometry of donor molecules, electrostatic potentials at the donor atoms and the steric effects on the formation of cocrystals was investigated as well as their influence on the final product stoichiometry. Additionally, the basicity of acceptor molecules has emerged as a highly important factor for the preparation of cocrystals with slightly weaker donors and for the synthesis of cocrystals with a tritopic halogen bond donor, in which three acceptor molecules are attached to the donor molecule

Cocrystallization of perfluoroiodobenzenes with simple pyridine derivatives – comparative evaluation of classical halogen bond donors

U sklopu disertacije pripravljeno je 37 novih kokristala jodperfluorbenzenâ i jednostavnih derivata piridina koji su strukturno i termički okarakterizirani. Po prvi puta su sustavno ispitana i uspoređena donorska svojstva komercijalnih jodperfluorbenzenâ i uočene su sličnosti i razlike u strukturama njihovih kokristala s jednostavnim derivatima piridina. Potvrđena je teza o 1,4-dijodtetrafluorbenzenu kao provjerenom i pouzdanom donoru halogenske veze koji tvori kokristale s 13 korištenih akceptora, dok je s 1,2-dijodtetrafluorbenzenom pripravljeno samo 5 kokristala. Ispitan je međuodnos geometrije molekula donora, iznosa elektrostatskih potencijala na donorskim atomima i prostornih ograničenja na nastajanje kokristala te njihov utjecaj na konačnu stehiometriju produkta. Također, bazičnost molekulâ akceptora istaknula se kao iznimno bitan faktor za pripravu kokristala s nešto slabijim donorima te kokristala s tritopičnim donorom halogenske veze, u kojemu su na molekulu donora vezane tri molekule akceptora.In this study, 37 novel cocrystals of iodoperfluorobenzenes and simple pyridine derivatives were prepared and structurally and thermally characterized. For the first time, donor properties of commercial iodoperfluorobenzenes were systematically examined and compared, and similarities and differences in their cocrystal structures with simple pyridine derivatives were observed. 1,4-diiodotetrafluorobenzene was proven as a reliable halogen bond donor with a total of 13 prepared cocrystals, while 1,2-diiodotetrafluorobenzene forms cocrystals with only 5 used acceptors. The relationship between the geometry of donor molecules, electrostatic potentials at the donor atoms and the steric effects on the formation of cocrystals was investigated as well as their influence on the final product stoichiometry. Additionally, the basicity of acceptor molecules has emerged as a highly important factor for the preparation of cocrystals with slightly weaker donors and for the synthesis of cocrystals with a tritopic halogen bond donor, in which three acceptor molecules are attached to the donor molecule

Rare Earth Elements Enrichment in the Upper Eocene Tošići-Dujići Bauxite Deposit, Croatia, and Relation to REE Mineralogy, Parent Material and Weathering Pattern

Tošići-Dujići bauxite deposit, situated in Dalmatian inlands, Croatia, contains minor remaining bauxite reserves. The deposit lies on Lower Eocene foraminiferal limestone and is covered by Upper Eocene Promina sediments. Bauxite samples were analyzed for textural, mineralogical, and geochemical features in order to determine absolute REE abundances and their relation to mineralogy, as well as to devise the origin of REE enrichment and to trace weathering and bauxitization paths of the parent material. The samples show total REE abundances up to 3500 mg/kg with significant HREE enrichment in some cases. All samples are gibbsitic with hematite and anatase as major phases. Kaolinite occurs in most of the samples, and goethite, böhmite, and nordstrandite are minor phases. Monazite-(Ce) and xenotime-(Y) were identified as detrital REE minerals as well as authigenic florencite-(Ce). In the REE most abundant sample, REE are most likely bound to Fe- and Ti-oxide phases as suggested by correlation analysis. Chemical weathering proxies show intensive weathering. Geochemical and textural data imply that the REE enrichment is influenced by intensive weathering (CIA 97.87–99.26) of detrital material, and also by possible deposition/redeposition of residual material potentially derived and mobilized from various sedimentary rocks of the area