Holistic approach to dissolution kinetics : linking direction-specific microscopic fluxes, local mass transport effects and global macroscopic rates from gypsum etch pit analysis

Dissolution processes at single crystal surfaces often involve the initial formation and expansion of localized, characteristic (faceted) etch-pits at defects, in an otherwise comparatively unreactive surface. Using natural gypsum single crystal as an example, a simple but powerful morphological analysis of these characteristic etch pit features is proposed that allows important questions concerning dissolution kinetics to be addressed. Significantly, quantitative mass transport associated with reactive microscale interfaces in quiescent solution (well known in the field of electrochemistry at ultramicroelectrodes) allows the relative importance of diffusion compared to surface kinetics to be assessed. Furthermore, because such mass transport rates are high, much faster surface kinetics can be determined than with existing dissolution methods. For the case of gypsum, surface processes are found to dominate the kinetics at early stages of the dissolution process (small etch pits) on the cleaved (010) surface. However, the contribution from mass transport becomes more important with time due to the increased area of the reactive zones and associated decrease in mass transport rate. Significantly, spatial heterogeneities in both surface kinetics and mass transport effects are identified, and the morphology of the characteristic etch features reveal direction-dependent dissolution kinetics that can be quantified. Effective dissolution velocities normal to the main basal (010) face are determined, along with velocities for the movement of [001] and [100] oriented steps. Inert electrolyte enhances dissolution velocities in all directions (salting in), but a striking new observation is that the effect is direction-dependent. Studies of common ion effects reveal that Ca2+ has a much greater impact in reducing dissolution rates compared to SO42−. With this approach, the new microscopic observations can be further analysed to obtain macroscopic dissolution rates, which are found to be wholly consistent with previous bulk measurements. The studies are thus important in bridging the gap between microscopic phenomena and macroscopic measurements

Limb-shaking transient ischemic attacks: case report and review of literature

BACKGROUND: Limb shaking Transient Ischemic Attack is a rare manifestation of carotid-occlusive disease. The symptoms usually point towards a seizure like activity and misdiagnosed as focal seizures. On careful history the rhythmic seizure like activity reveals no Jacksonian march mainly precipitated by maneuvers which lead to carotid compression. We here present a case of an elderly gentleman who was initially worked up as suffering from epileptic discharge and then later on found to have carotid occlusion. CASE PRESENTATION: Elderly gentleman presented with symptoms of rhythmic jerky movements of the left arm and both the lower limbs. Clinical suspicion of focal epilepsy was made and EEG, MRI-Brain with MRA were done. EEG and MRI-Brain revealed normal findings but the MRA revealed complete occlusion of right internal carotid artery. On a follow-up visit jerky movements of the left arm were precipitated by hyperextension and a tremor of 3–4 Hz was revealed. Based on this the diagnosis of low flow TIA was made the patient was treated conservatively with adjustment of his anti-hypertensive and anti-platelet medications. CONCLUSION: Diagnosis of limb-shaking TIA is important and should be differentiated from other disorders presenting as tremors. Timely diagnosis is important as these patients are shown to benefit from reperfusion procedures either surgical or radiological reducing their risk of stroke

Factors Affecting Bubble Size in Ionic Liquids

This study reports on understanding the formation of bubbles in ionic liquids (ILs), with a view to utilising ILs more efficiently in gas capture processes. In particular, the impact of the IL structure on the bubble sizes obtained has been determined in order to obtain design principles for the ionic liquids utilised. 11 ILs were used in this study with a range of physico-chemical properties in order to determine parametrically the impact on bubble size due to the liquid properties and chemical moieties present. The results suggest the bubble size observed is dictated by the strength of interaction between the cation and anion of the IL and, therefore, the mass transport within the system. This bubble size – ILs structure–physical property relationship has been illustrated using a series of QSPR correlations. A predictive model based only on the sigma profiles of the anions and cations has been developed which shows the best correlation without the need to incorporate the physico-chemical properties of the liquids. Depending on the IL, selected mean bubble sizes observed were between 56.1 and 766.9 μm demonstrating that microbubbles can be produced in the IL allowing the potential for enhanced mass transport and absorption kinetics in these systems

The Structure of the National Department of the Diet of Galicia and Lodomeria from 1861 to 1918

Tekst pracy licencjackiej podejmuje próbę przybliżenia czytelnikowi prawnych oraz organizacyjnych fundamentów dla istnienia i działania organu wykonawczego Królestwa Galicji i Lodomerii w latach 1861 - 1918. Autor analizując współczesną literaturę naukową oraz materiał normatywny i archiwalny z badanego okresu stara się opisać i scharakteryzować pod względem strukturalnym wszystkie administracyjne komórki funkcjonujące w Wydziale Krajowym Sejmu Galicyjskiego. Początek pracy oraz rozdział pierwszy skupiają się na przybliżeniu czytelnikowi charakterystyki okresu oraz autonomii galicyjskiej a także kulisy powstania Sejmu Galicyjskiego i jego Wydziału Krajowego. Następnie podjęta jest próba przyjrzenia się dzialałności wszystkich urzędników organu - od Marszałka, poprzez członków Wydziału jako naczelników departamentów na sługach Wydziału kończąc. Rozdział trzeci skupia się na okresie schyłkowym działalności Wydziału Krajowego w obliczu I Wojny Światowej oraz na jego formalnym zniesieniu. Praca zawiera również krótki opis następcy prawnego organu - Tymczasowego Wydziału Samorządowego.The text of this Bachelor's Thesis attempts to approximate the legal and organizational foundations for the existence and actions taken by the executive body of the Kingdom of Galicia and Lodomeria from 1861 to 1918. Author, by analyzing the modern academical literature as well as the legal and archival sources from the historical period that is being analyzed, is making an attempt to describe, from the structural point of view, every administrative cell that functioned within the National Department of the Diet of Galicia and Lodomeria. The Introduction and the Chapter First focus on the reality of the historical era and the Galician autonomy as well as the historical and legal background of the creation of the Diet of Galicia and Lodomeria and its' National Department. Afterwards, an effort is made to look closely at the activity of every official of the executive body - starting with the Marshal followed by members of the National Department working as the heads of particular inside departments and ending with the minor service staff. Chapter Three focuses on the final period of the National Department existence, its status facing the World War I, and finally - its formal disassembling. The Thesis also contains a short description of the National Department legal successor - the Temporary Autonomy Department

Chess in Vladmir Nabokov's works

Niniejsza praca opisuje w jaki sposób zainteresowanie szachami wpłynęło na twórczość Vladimira Nabokova, a także czym charakteryzuje się jego stosunek do tej gry, w porównaniu do innych autorów.The following BA thesis describes how the influence of Nabokov's interest in chess on his works and also his attitude towards this game in comparison to other authors

Konwersacyjny kontekst przełączania językowego w zadaniu nazywania obrazków

Celem pracy było sprawdzenie, czy wskazówki słuchowe w zadaniu nazywania obrazków będą rozpoznane jako bardziej trafne ekologicznie i wpłyną na redukcję kosztu przełączania języków w zadaniu nazywania obrazków pośród dwujęzycznych badanychThe present study was aimed at investigating if auditory cues in picture naming task would be considered as more ecologically valid cues and would reduce the switch cost in picture naming task of Polish-English bilingual

Smart Contract in view of the general principles of the Civil Code

Praca skupia się na zbadaniu instytucji smart contractu oraz analizie poszczególnych przepisów części ogólnej oraz części ogólnej prawa zobowiązań kodeksu cywilnego. Autor podejmuje próbę zdefiniowania terminu "smart contract" na płaszczyźnie doktrynalnej oraz sprawdzenia i opisania ewentualnych różnic między umową tradycyjną a smart contractem. Przedmiotem pracy jest także ocena czy kodeks cywilny wymaga dostosowania dla właściwej regulacji obrotu smart contractami, czy jego obecny kształt jest wystarczający. Pracę wieńczy analiza możliwości zakwalifikowania smart contract'u jako wzorca umownego.Master's thesis focuses on examining the smart contract institution and analyzing individual provisions of the general part and part of the general law of obligations of the Civil Code. The author attempts to define the term "smart contract" on the doctrinal level and to check and describe possible differences between a traditional contract and a smart contract. The subject of the Master's Thesis is also the assessment whether the Civil Code requires adjustment for proper regulation of trading in smart contracts, whether its present shape is sufficient. The Master's Thesis is crowned with the analysis of the possibility of qualifying smart contract as a standard contract

Effect of Infrared Light on Protein Behavior in Contact with Solid Surface

Adsorption of proteins at a solid surface affects characteristics of the surface (e.g. its biocompatibility) and functionality of the immobilized biomacromolecules. The latter is defined by the type of binding sites, protein conformation and its structural flexibility that enable functional motions to occur. Protein motions are only possible at certain level of hydration. Furthermore, water molecules act as lubricant facilitating sliding along solid surface. In this work we explore the potential of a remote physical trigger –a non-ionizing infrared radiation (IR) to affect protein-surface interactions. We report on IR-induced changes of hydrophilicity of the protein coatings on silica nanoparticles, impact of IR on monitored in-situ dynamic adsorption of proteins on silica surface and effect of IR on conformational state of adsorbed proteins. Our results indicate that IR can protect proteins from surface denaturation depending on the presence of strongly hydrated amino acid residues. Preservation of native fold results in protein coatings of higher hydrophilicity. IR can also facilitate displacement of surface activespecies that became adsorbed to protein apolar compartments and couldotherwise promote denaturation. Apart from supporting native conformation, their removalincreases protein-water interfacial tension and therefore promotes aggregation (hydrophobic attraction) of the protein-coated nanoparticles. By its ability to affect protein conformational state and interfacial characteristics (such as effective protein-water affinity) IR radiation can therefore modulate protein interactions