Supramolecular layers and versatile packing modes: the solid state behavior of ortho, ortho-linked bisphenols

A series of ortho-ortho-linked bisphenols featuring electron-withdrawing groups (EWGs) attached to the phenolic rings is reported. Their respective molecular structures and packing behaviors have been studied by X-ray diffraction, comparatively discussed and put into relation with the unsubstituted mother compound. Except for the mother compound, the molecular structures of all bisphenols studied here exhibit distorted aromatic moieties. Hence, the substituents studied here prevent proximal positioning of phenolic units and the formation of strong O-H···O hydrogen bonds. In the packing of the underivatized bisphenol we found a strand-like molecular arrangement featuring strong O-H···O hydrogen bonds and extensive edge-to-face contacts (C-H···π) between the bisphenol molecules. The introduction of EWGs to the aromatic moieties changes these intermolecular interactions into face-to-face contacts resulting either in bisphenol stacks or handshake-like motifs between two bisphenol molecules. In both cases, the C-H···π interactions are more or less replaced by C-H···O contacts as the prevalent non-covalent interaction. In the packing of two nitro bisphenols in their DMSO inclusion compounds an exciting layered arrangement is observed, which also matches with the pronounced foliated habitus of their crystals. Additionally, proton NMR was used to establish the binding coefficients between the respective bisphenols and DMSO in solution

Solid-state nuclear magnetic resonance spectroscopy of cements

Cement is the ubiquitous material upon which modern civilisation is built, providing long-term strength, impermeability and durability for housing and infrastructure. The fundamental chemical interactions which control the structure and performance of cements have been the subject of intense research for decades, but the complex, crystallographically disordered nature of the key phases which form in hardened cements has raised difficulty in obtaining detailed information about local structure, reaction mechanisms and kinetics. Solid-state nuclear magnetic resonance (SS NMR)spectroscopy can resolve key atomic structural details within these materials and has emerged as a crucial tool in characterising cement structure and properties. This review provides a comprehensive overview of the application of multinuclear SS NMR spectroscopy to understand composition–structure–property relationships in cements. This includes anhydrous and hydrated phases in Portland cement, calcium aluminate cements, calcium sulfoaluminate cements, magnesia-based cements, alkali-activated and geopolymer cements and synthetic model systems. Advanced and multidimensional experiments probe 1 H, 13 C, 17 O, 19 F, 23 Na, 25 Mg, 27 Al, 29 Si, 31 P, 33 S, 35 Cl, 39 K and 43 Ca nuclei, to study atomic structure, phase evolution, nanostructural development, reaction mechanisms and kinetics. Thus, the mechanisms controlling the physical properties of cements can now be resolved and understood at an unprecedented and essential level of detail

Property Tax in Slovak Republic

Tato bakalářská práce se věnuje dani z nemovitých věcí na Slovensku a analýze pravomocí, které jim byly přiděleny v procesu fiskální decentralizace. První část práce rozebírá veřejní správu a s ní související reformní kroky a fiskální decentralizaci. Druhá část práce se zabývá dvěma zákony, které upravovaly daň z nemovitých věcí od roku 1993 až po současnost a analýzou pravomocí, které obce ve sledovaném období vydáním obecně závazných nařízení využily. Poslední části je zhodnocení využívání získaných pravomocí.This bachelor thesis is about property tax in Slovakia and analysis of authorities, which were granted to them in the process of fiscal decentralization. The first part of the bachelor thesis analyzes public service and its reformative steps and the fiscal decentralization. The second part of the bachelor thesis writes about 2 laws, which governed the property tax since the year 1993 to present and about analysis of authorities, which municipalities used in selected period by publication of the general binding regulations. The last part is a summary of using the granted authorities.Táto bakalárska práca sa venuje dani z nehnuteľností na Slovensku a analýze právomocí, ktoré im boli pridelené v procese fiškálnej decentralizácie. Prvá časť práce rozoberá verejnú správu a s ňou súvisiace reformné kroky a fiškálnu decentralizáciu. Druhá časť práce sa zaoberá dvomi zákonmi, ktoré upravovali daň z nehnuteľností od roku 1993 až po súčasnosť a analýzou právomocí, ktoré obce v sledovanom období vydaním všeobecne záväzných nariadení využili. Poslednou časťou je zhodnotenie využívania získaných právomocí

Corporate taxation in selected EU countries

Tato diplomová práce se zabývá daní z příjmu právnických osob vy vybraných státech Evropské unie, mezinárodním zdaněním pasívních příjmů a harmonizaci v oblasti přímých daní. První část práce je zaměřena na daň z příjmu, postup stanovení základu daně a na jeho následnou úpravu. Druhá část bude obsahovat komparaci rozličných oblastí týkajících se daně z příjmu (vztah k hrubému domácímu produktu, výška příjmů, daňový mix a daňová kvóta). Součástí třetí části práce bude mezinárodní zdanění dividend, úroků a licenčních poplatků a vzájemná komparace smluv o zamezení dvojího zdanění. Poslední část se bude soustředit na harmonizaci přímých daní.This diploma thesis deals with corporate income tax in selected countries of the European Union, international taxation of passive income and harmonization in the field of direct taxes. The first part of the work is focused on income tax, the procedure for determining the tax base and its subsequent adjustment. The second part will contain a comparison of different areas related to income tax (relation to gross domestic product, amount of income, tax mix and tax quota). The third part of the thesis will include the international taxation of dividends, interest and royalties and the mutual comparison of double taxation treaties. The last part of the thesis will focus on the harmonization of direct taxes.Táto diplomová práca sa zaoberá daňou z príjmu právnických osôb vo vybraných štátoch Európskej únie, medzinárodným zdanením pasívnych príjmov a harmonizáciou v oblasti priamych daní. Prvá časť práce je zameraná na daň z príjmu, postup stanovenia základu dane a na jeho následnú úpravu. Druhá časť bude obsahovať komparáciu rozličných oblastí týkajúcich sa dane z príjmu (vzťah k hrubému domácemu produktu, výška príjmov, daňový mix a daňová kvóta). Súčasťou tretej časti práce bude medzinárodne zdanenie dividend, úrokov a licenčných poplatkov a vzájomná komparácia zmlúv o zamedzení dvojitého zdanenia. Posledná časť práce sa bude sústrediť na harmonizáciu priamych daní

Hydrogen bonding and vibrational spectra in kaolinite-dimethylsulfoxide and -dimethylselenoxide intercalates - A solid-state computational study

The aims of this study were to obtain accurate structural information on the dimethyl sulfoxide (DMSO) and dimethylselenoxide (DMSeO) kaolinite intercalates, paying close attention to the hydrogen-bond geometries, and to provide a detailed interpretation of the individual vibrational modes of intercalates under study and relate their energies to the formation of the hydrogen bonds. Accurate positions of all the atoms in the structures of kaolinite:dimethylsulfoxide (K:DMSO) and kaolinite:dimethylselenoxide (K:DMSeO) intercalates have been obtained by the total energy minimization in solid state at density functional theory (DFT) level of the theory. The bond distances and angles in the kaolinite 1:1 layer are in good agreement with those reported in the most recent single-crystal refinement of kaolinite. Computed geometries of DMSO and DMSeO agree well with the high-quality diffraction data and independent theoretical ab initio calculations. The organic molecules are fixed in the interlayer space mainly by three moderately strong O - H...O hydrogen bonds, of different strengths, with the O...O contact distances being within 2.739-2.932 Å (K:DMSO) and 2.681-2.849 Å (K:DMSeO). Substantially weaker C - H...O and O - H...S(Se) contacts play only a supporting role. The optimized atomic coordinates were used to calculate the individual vibrational modes between 0 and 4000 cm. The maximum red shifts of the OH-stretching modes caused by the formation of the O - H...O hydrogen bonds were 407 cm (KaDMSO) and 537 cm (K-DMeSO), respectively. The Al - O - H bending modes are spread over the large interval of 100-1200 cm, but the dominant contributions are concentrated between 800 and 1200 cm. Theoretically calculated energies of the OH- and CH-stretching modes show good agreement with the previously published figures obtained from the infrared and Raman spectra of these intercalates

Mathematical Education and Developing the Emotional and Social Competencies of the Child in Pre-primary and Primary Education in Slovakias

Mathematical education at the pre-primary stage sets out its aims which are predominantly focussed on the area of developing the cognitive side of the child’s personality. This area becomes the focus of relevant curricular documents for mathematical education, on the one hand, and influences the actual teaching of mathematics in practice, on the other. Meaningful and effective cross-curricular mathematical education opens a new space for developing the emotional and social skills of the child. The above aspect of mathematical education has the potential to become a determining factor in creating a positive attitude towards mathematics

Influence of synthesis conditions on the formation of a Kaolinitemethanol complex and simulation of its vibrational spectra

Kaolinite is often used as a base for the synthesis of new organo-mineral nanomaterials designed for applications in industry and in environmental protection. To make the mineral structure more likely to interact with organic molecules, a kaolinite-methanol complex (KM) can be used. In the present study, different experimental procedures were tested to investigate the formation of the KM. The kaolinitedimethyl sulfoxide intercalation compound (KDS), either wet or dried, was used as a pre-intercalate. The samples obtained were characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, CHNS elemental analysis, C CP-magic angle spinning nuclear magnetic resonance (MAS NMR), and Al and Si MAS NMR techniques. The method of density functional theory with dispersion corrections (DFT-D2) was used to explain the structure and to simulate the vibrational spectra of KM. Theoretical results were compared with experimental data. The most effective formation of the KM (d = 11.1 Å wet; d = 8.7 Å dried) was observed when the dried KDS precursor was used. In such conditions the degree of intercalation reached ~98% after 24 h of reaction time. As indicated by the CHNS elemental analysis, ~1/6 of the inner-surface OH groups were grafted by OCH groups. The esterification reaction was less efficient at higher temperatures or when wet KDS was used. In the latter case, the excess of very polar dimethyl sulfoxide molecules prevented intercalation of methanol and further grafting. Detailed analysis of the results of theoretical simulations revealed that the reaction of the KDS with methanol led to the formation of kaolinite with both grafted methoxy groups and intercalated methanol, and water molecules in the interlayer space. The spectra calculated revealed the contribution of individual vibrational modes into the complex bands, i.e. the energy of C-H vibrations was in the order:vCH> vCH> vCH> vCH