Physicochemical characterisation of ionic liquids and lactones binary mixtures and their application as electrolytes for lithium-ion batteries

U  ovoj  doktorskoj  disertaciji  ispitivani  su  elektroliti  na  bazi binarnih  smeša  imidazolijumovih  jonskih  tečnosti  i  laktona  koji su  pogodni  za  primenu  u  litijum-jonskim  baterijama.  Fizičkohemijska  svojstva  binarnih  smeša  jonskih  tečnosti  na  bazi imidazolijum katjona i bis (trifluorometilsulfonil)imidnog anjona i laktona ispitana su u celom opsegu molskih udela i na različitim temperaturama.  Na  osnovu  izmerenih  gustina,  viskoznosti  i električne  provodljivosti  izračunati  su  različiti  fizičko-hemijski parametri i diskutovane  interakcije između komponenata smeša. Ispitana  je  termička  i  elektrohemijska  stabilnost  odabranih elektrolita.  Na  osnovu  dobijenih  rezultata,  prvo  je  odabran odgovarajući  lakton  koji  je  kasnije  kombinovan  sa  jonskim tečnostima  na  bazi  imidazola,  koje  se  međusobno  razlikuju  u dužini  bočnog  niza  katjona.  Na  osnovu  fizičko-hemijskih svojstava  na  različitim  temperaturama  i  pri  različitim  sastavima binarnih  smeša  diskutovan  je  način  organizacije  njihovih komponenata.  U  binarne  smeše  koje  su  se  pokazale  kao najperspektivnije  sa  stanovišta  električne  provodljivosti, viskoznosti,  elektrohemijske  stabilnosti  i  (ne)zapaljivosti  dodata je litijumova so. Tako dobijeni ternarni sistemi su okarakterisani u zavisnosti od koncentracije litijumove soli. Odabrani elektroliti upotrebljeni su za ispitivanje performansi litijum-jonske ćelije sa elektrodama  na  bazi  anatas  TiO2  nanocevi.  Cikličnom voltametrijom  i  galvanostatskim  cikliranjem  ispitane  su performanse ćelije u toku 350 ciklusa punjenja i pražnjenja. Na osnovu   ciklovoltametrijskih  merenja  izračunati  su  koeficijenti difuzije jona Li  + i energija aktivacije za difuziju.  Kombinacijom jonskih  tečnosti  i  laktona  moguće  je  dobiti  elektrolite  smanjene viskoznosti,  povećane  električne  provodljivosti,  povećane termičke  stabilnosti  usled  međusobnog  stabilizacionog  efekta laktona na imidazolijumove jonske tečnosti.In  this  doctoral  dissertation,  binary  mixtures  based  on  imidazolium  ionic  liquids  with  lactones  were  tested  for  use  in lithium-ion  batteries.  The  physicochemical  properties  of  binary  mixtures  of  imidazolium  based  ionic  liquids  with  bis (trifluoromethylsulfonyl)imide  anions  and  lactones  were  examined  throughout  the  whole  composition  range  and  at  different temperatures. Based on the measured densities, viscosity  and electrical conductivity, various physical chemical parameters  and discrete interactions between the components of the mixture are  calculated.  Thermal  and  electrochemical  stability  of  selected  binary  mixtures  were  examined.  Based  on  obtained  results  was  selected lactone  which is later combined with imidazolium based  ionic liquid,  differing from each other in the length of the cation. Based  on  the  physico-chemical  properties  at  different  temperatures and in the different compositions of binary mixtures, the way of organizing their components is discussed. Lithium salt  is added to the binary mixtures that have been shown as the most perspective  from  the  standpoint  of  electrical  conductivity, viscosity,  electrochemical  stability  and  (non)flammability.  The  resulting  ternary  systems  are  characterized  according  to  the concentration of lithium salt.  The selected electrolytes were used to test the performance of the lithium-ion cell with anatase TiO2 nanotubular  electrodes.  Cyclic  voltammetry  and  galvanostatic  cycling  tested  the  cell's  performance  during  the  350  charge  and discharge  cycles.  Based  on  cyclic  voltammetric  measurements, the  Li + ion  diffusion  coefficients  and  activation  energies  for diffusion  were  calculated.  Combination  ionic  liquid  and  lactone could  be  obtained  electrolytes  with  lower  viscosity,  higher electrical  conductivity,  improved  thermal  stability  due  to stabilization effect of lactone on imidazolium based ionic liquids

Utjecaj sustava držanja na bolesti papaka i postotak izlučenja u krava holštajnske pasmine

The objectives of this research were to investigate the effect of the housing system (tie-stall and free-stall barns) on the prevalence of hoof diseases/disorders, as well as on the percentage of culling in 6,348 Holstein dairy cows from 5 farms. During the three months of research the hoof care service on all farms collected records of causes of lameness, diagnoses and treatments. Functional and corrective hoof trimming was conducted by a professional farm trimmer. When all the registered diseases/disorders were observed as a percentage (all diseases = 100%), it was noticed that both housing systems were similarly affected by the same diseases/disorders. In this regard, White Line Disease occurred in both systems in prevalence of 0.5% - 1%, Toe Ulcer and Necrosis in 3% - 6%, Rusterholz Ulcer / Sole Ulcer in 20% - 23%, Digital Dermatitis in 18% - 20%, Interdigital Hyperplasia / Tyloma in 10% - 12%, Panaritium / Interdigital Phlegmon in 0.7% - 0.77%, while the prevalence of Mechanical Injury was negligible and in similar amounts - 0.2% - 0.5%. Cows in the free-stall barns were much more burdened with Dermatitis Interdigitalis / Heel Erosion Disease (39.11%) compared to cows in the bound housing system (20.40%). In contrast, diagnosed acute, chronic and haemorrhagic Laminitis was significantly more pronounced in the tie-stall barns (18.61%) than in the free-stall barns (0.88%). In the statistical analysis conducted, statistically significantly more diseases/disorders were registered in the tie-stall system than in the free housing system (P0.05).Cilj je istraživanja bio utvrditi utjecaj držanja (vezani ili slobodni sustav) na pojavnost bolesti i promjena na papcima, kao i na postotak izlučenja u krava holštajnske pasmine. Uključeno je 6348 krava s pet farmi, za koje su tijekom tri mjeseca prikupljeni podaci o obradi i njezi papaka, uzrocima šepavosti, dijagnozama te redovitim liječenjima. Funkcionalno i korektivno obrezivanje papaka provele su osobe educirane za to. Promotre li se svi registrirani poremećaji i bolesti postotno (sve bolesti = 100 %), zapaža se da su oba sustava držanja bila u sličnoj mjeri opterećena istim bolestima. U skladu s tim, bolest bijele linije opažena je u oba sustava, s pojavnošću od 0,5 do 1%, čir i nekroza papka od 3 do 6 %, Rusterholzov čir / Ulcus soleae od 20 do 23 %, digitalni dermatitis od 18 do 20 %, interdigitalna hiperplazija / tilom od 10 do 12 %, panaricij / interdigitalna flegmona od 0,7 do 0,77 %, dok je postotak mehaničkih ozljeda bio vrlo sličan i zanemariv (0,2 – 0,5 %). Krave u slobodnom sustavu držanja bile su mnogo više opterećene bolešću interdigitalni dermatitis / erozija pete (39,11 %) u odnosu na krave u vezanom sustavu držanja (20,40 %). Suprotno tomu, pojavnost akutnog, kroničnog i hemoragijskog laminitisa bila je znakovito veća u vezanom sustavu držanja (18,61 %) nego u slobodnom (0,88 %). Na osnovi provedenih statističkih proporcija i Z-testa tijekom istraživanog razdoblja, registrirano je statistički znakovito više bolesti i poremećaja u vezanom sustavu držanja nego u slobodnom (P0,05)

Učinak dipping profila gestacijske hipertenzije na majčine simptome i fizikalne nalaze, porođajnu težinu i prijevremeni porođaj

The study aimed to determine if the non-dipping pattern of blood pressure (BP) influences preterm delivery in gestational hypertension (GH), but also maternal clinical findings and birth weight. Sixty women with GH, i.e. 30 women with a dipping BP profile (control group) and 30 non-dippers (study group), were included in the study. Echocardiography was performed in all subjects, as well as ambulatory blood pressure monitoring (ABPM) during third trimester. ABPM was repeated 6-8 weeks after delivery. Thirteen women with preterm delivery were classified as non-dippers and only four as dippers (p=0.01). The average and peak systolic and diastolic night-time BP had negative linear correlation with birth weight (p<0.0005). Total vascular resistance (p<0.0005) and mass index (p=0.014) were significantly higher as compared with women with term delivery, while ejection fraction (EF) (p=0.007) and circumferential systolic velocity (p=0.042) were significantly reduced in the preterm delivery group. Multivariate binary logistic regression identified the average night-time systolic BP, left ventricular mass index and EF as independent predictors of preterm delivery. Study results suggested a relationship of the non-dipping BP pattern in GH with preterm delivery, birth weight, and maternal clinical findings.Cilj ovoga istraživanja bio je utvrditi povezanost non-dipping profila krvnog tlaka (KT) s prijevremenim porođajem, porođajnom težinom novorođenčeta te kliničkim i ehokardiografskim parametrima kod žena s gestacijskom hipertenzijom (GH). Istraživanje je obuhvatilo 60 žena s GH, 30 s dipping profilom KT (kontrolna skupina) i 30 non-dippera (ispitna skupina). Sve žene podvrgnute su kompletnoj ehokardiografiji i 24-satnom ambulantnom praćenju krvnog tlaka (ambulatory blood pressure monitoring, ABPM) tijekom trećeg trimestra, a ABPM je ponovljen 6-8 tjedana nakon porođaja. Ukupno 17 žena imalo je prijevremeni porođaj. Trinaest žena s prijevremenim porođajem imalo je non-dipping profil KT, dok su samo četiri žene imale dipping profil KT (0,01). Prosječni i maksimalni sistolički i dijastolički noćni KT imali su negativnu linearnu korelaciju s porođajnom težinom (p<0,0005). Ukupna vaskularna rezistencija (p<0,0005) i indeks mase miokarda lijeve klijetke (p=0,014) bili su znatno viši u skupini žena s prijevremenim porođajem, dok su parametri sistoličke funkcije, tj. ejekcijska frakcija (EF) (p=0,007) i brzina cirkumferentnog skraćenja miokarda lijevog ventrikla (p=0,042) bili statistički značajno sniženi u skupini žena s prijevremenim porođajem. Multivarijatna regresijska analiza pokazala je da su prosječni noćni sistolički KT, indeks mase lijevog ventrikla i EF identificirani kao nezavisni prediktori prijevremenog porođaja. Rezultati istraživanja pokazali su da postoji povezanost između non-dipping profila KT s prijevremenim porođajem, porođajnom težinom novorođenčeta i poremećajem hemodinamskog statusa majke u GH

Thermo-Analytical and Compatibility Study with Mechanistic Explanation of Degradation Kinetics of Ambroxol Hydrochloride Tablets under Non-Isothermal Conditions

Ambroxol hydrochloride (AMB), used as a broncho secretolytic and an expectorant drug, is a semi-synthetic derivative of vasicine obtained from the Indian shrub Adhatoda vasica. It is a metabolic product of bromhexine. The paper provides comprehensive and detailed research on ambroxol hydrochloride, gives information on thermal stability, the mechanism of AMB degradation, and data of practical interest for optimization of formulation that contains AMB as an active compound. Investigation on pure AMB and in commercial formulation Flavamed® tablet (FT), which contains AMB as an active compound, was performed systematically using thermal and spectroscopic methods, along with a sophisticated and practical statistical approach. AMB proved to be a heat-stable and humidity-sensitive drug. For its successful formulation, special attention should be addressed to excipients since it was found that polyvinyl pyrrolidone and Mg stearate affect the thermal stability of AMB. At the same time, lactose monohydrate contributes to faster degradation of AMB and change in decomposition mechanism. It was found that the n-th order kinetic model mechanistically best describes the decomposition process of pure AMB and in Flavamed® tablets

Effect of Zwitterionic Additive on Electrode Protection through Electrochemical Performances of Anatase TiO₂ Nanotube Array Electrode in Ionic Liquid Electrolyte

In this work, a functionalized zwitterionic (ZI) compound 1-butylsulfonate-3-methylimidazole (C1C4imSO3) was synthesized and tested as an additive to LiTFSI/C2C2imTFSI ionic liquid-based electrolytes for lithium-ion batteries. The structure and purity of C1C4imSO3 were confirmed by NMR and FTIR spectroscopy. The thermal stability of the pure C1C4imSO3 was examined by simultaneous thermogravimetric–mass spectrometric (TG–MS) measurements and differential scanning calorimetry (DSC). The LiTFSI/C2C2imTFSI/C1C4imSO3 system was tested as a potential electrolyte for lithium-ion batteries by using anatase TiO2 nanotube array electrode as the anode material. This electrolyte with 3% C1C4imSO3 showed significant improvement of lithium-ion intercalation/deintercalation properties, such as capacity retention and Coulombic efficiency compared to electrolyte without additive

Electrochemical study of anatase TiO2 nanotube array electrode in electrolyte based on 1,3-diethylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid

The density, viscosity and electrical conductivity of ionic liquid 1,3-diethylimidazolium bis(trifluoromethylsulfonyl)imide, (C2C2imTFSI), and 0.5 M solution of LiTFSI in C2C2imTFSI were determined at different temperatures. The LiTFSI/C2C2imTFSI system was tested as a possible electrolyte for lithium-ion batteries by using anatase TiO2 nanotube array electrode as anodematerial for the first time. The electrochemical testing has shown not only the improvement of lithium-ion insertion/deinsertion properties by increasing temperature but also the existence of a decomposition of the electrolyte, detecting the change of colour. The decomposition of electrolyte leads to the formation of a film on the surface of the electrode which improves Coulombic efficiency during cycling

Povezanost između uzrasta pri prvom teljenju i proizvodnje u prvoj laktaciji sa osobinama dugovečnosti kod mlečnih krava

The objective of this research was to determine the association between age at first calving (AFC) and milk production in the first lactation of longevity traits for Holstein cows. The research was conducted on 2307 cows raised on 4 farms in AP Vojvodina. The cows were culled in the period from 2017 to 2018. The cows belonged to the group of Holstein Friesian breed of cattle. Cow longevity was observed using three parameters: number of lactations (NL), lifetime milk yield (LMY) and length of productive life (LPL). The research involved the influence of the farm on which the animals realized their production, the season of first calving. A mean value obtained for the length of productive life in the analysed population was 1207 days (3.30 years on average). During this period the animals on average realized 2.45 lactations and produced on average 18798 kg milk. All studied traits showed a high level of variability. From these data, the study sought to determine the influence of factors on the traits of longevity, our research present that studied factors showed high statistical significance on these traits except in the case of the season of first calving where a statistical significance effect wasn't observed. The season of first calving did not affect the animal traits for longevity and, generally, didn't affect the calving interval. Regarding the obtained correlation data between age at first calving and length of productive life, it can be concluded that belated AFC leads to reduced reproductive performance.Sprovedeno istraživanje imalo je za cilj da utvrdi povezanost između uzrasta pri prvom teljenju i proizvodnje mleka u prvoj laktaciji sa osobinama dugovečnosti za krave holštajn-frizijske rase. Istraživanjem je obuhvaćeno 2307 krava, sa 4 različite farme sa teritorije AP Vojvodine. Krave su izlučene u periodu od 2017 do 2018 godine. Dugovečnost krava je posmatrana kroz tri pokazatelja: broj ostvarenih laktacija (NL), životna količina proizvedenog mleka (LMY) i dužina produktivnog života (LPL). Prosečno trajanje produktivnog života za sva grla uključena u analizu iznosilo je 1207 dana (3.30 godine u proseku). Grla obuhvaćena analizom u toku svog produktivnog života su prosečno proizvela 18798 kg mleka. Broj laktacija koje je svako grlo prosečno ostvarilo u toku trajanja svog produktivnog života iznosio je 2.45, pri čemu su svi ispitani parametri pokazali visok nivo varijabilnosti. U istraživanju su ispitani fiksni uticaji farme na kojoj je grlo proizvodilo, uzrasta pri prvom teljenju, sistema proizvodnje i sezone pri prvom teljenju na osobine dugovečnosti i međutelidbeni interval, korišćenjem linearnog modela. Na osnovu rezultata dobijenih istraživanjem, fiksni faktori su pokazali visoku statističku značajnost za ispitivane osobine, osim u slučaju sezone pri prvom teljenju, gde nije ispoljena statistička značajnost za osobine obuhvaćene istraživanjem. Na osnovu rezultata, utvrđena je povezanost između uzrasta pri prvom teljenju i dužine produktivnog života, pri čemu se može zaključiti da su kraći produktivni život imale životinje koje su se kasnije telile

Physicochemical Investigations of a Binary Mixture Containing Ionic Liquid 1-Butyl-1-methylpyrrolidinium Bis(trifluoromethylsulfonyl)imide and Diethyl Carbonate

Densities, viscosities, and electrical conductivities were determined and discussed for a binary mixture containing 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid, [bmpyrr][NTf2], and diethyl carbonate (DEC) as a function of temperature (T = 293.15-323.15 K) at atmospheric pressure (p = 0.1 MPa) over the entire range composition. Based on experimental density data, the related excess molar volumes were calculated and fitted using Redlich-Kister's polynomial equation. The Casteel-Amis equation was used to correlate data obtained from electrical conductivity measurements. The effect of viscosity on electrical conductivity was discussed by the Walden rule. The Bahe-Varela theory, derived from the the pseudo-lattice model, has been successfully applied to explain the influence of the mixture composition on electrical conductivity. Based on physicochemical characterization supported with computational simulations for binary mixtures ([bmpyrr][NTf2] + DEC), the interactions between these components were discussed. © 2019 American Chemical Society

Greener sample preparation method for direct determination of Cd(II) and Pb(II) in river sediment based on an aqueous biphasic system with functionalized ionic liquids

Although sample preparation, as an unavoidable step of the analytical process should be simple, it is very often identified as a bottleneck. Simplicity of sample preparation based on cost-effective and non-hazardous materials is mandatory for any sustainable and environmental friendly approach. Aqueous biphasic systems (ABS), based on functionalized ionic liquids (FILs) are acceptable alternatives to classical extraction procedures, due to the replacement of organic solvent with diluted aqueous-soluble ionic liquids. In this work, two water soluble FILs based on 2-mercaptobenzothiazolate anion, [mbt]: 1-butyl-3-methylimidazolium [mbt] ([bmim][mbt]) and 1-ethyl-3-methylimidazolium [mbt] ([emim][mbt]), were designed and synthesized in order to selectively extract Cd(II) and Pb(II) from the river sediment. It was found that [mbt]– anion acts as the ligand and forms complexes with Cd(II) and Pb(II) which are responsible for their efficient extraction, while cation is more responsible for the formation of ABS. Partition coefficients of 408 and 180 for Cd(II) and Pb(II), respectively, were obtained using ABS based on [bmim][mbt]. Direct extraction of Cd(II) and Pb(II) from the river sediment has been investigated and obtained optimal conditions are: 60 min direct contact of the aqueous solution of [bmim][mbt] and the sediment sample at 90 °C, followed by formation of ABS upon addition of potassium citrate. Using AGRE and AGREEprep tools greenness of the proposed method for direct extraction of Cd(II) and Pb(II) from the sediment are calculated. Obtained values of 0.69 and 0.71 for Cd(II) and Pb(II) extraction, respectively, showed a high level of the greenness of the proposed method