This thesis deals with black carbon, its characteristic features and with its occurrence in chernozemic soils. In particular, this thesis deals with methods, which can study presence of black carbon in soils. The presence of black carbon and the whole composition of soil organic matter of three chernozemic soils in Czechia (Zeměchy, Tursko, Syrovice) is examined by 13 C NMR spectroscopy. Anthracological analysis of charcoal from fossil chernozems of Zemechy loess ravine deals with pedogenesis of chernozems and development of Quaternary vegetation in Central Europe. Coniferous tree species of Pinus sp., Pinus cf. cembra, Larix/Picea, Juniperus a Vaccicium, i.e. cold- and drought-tolerant taxa, were identified by anthracological analysis of soils of Zemechy loess ravine. The identified species suggest that the landscape around Zemechy was probably formed by parkland taiga. According to 13 C NMR spectroscopy, soil organic matter of fossil chernozem of Zemechy loess ravine consists particularly of alkyl and O-alkyl carbon. Aromatic carbon is also significant. O-alkyl carbon is the most important in the recent chernozems of Tursko and Syrovice. Aromatic carbon has the smallest proportion in both chernozems. The presence of aromatic carbon in chernozem of Tursko is the smallest of all analyzed soils. The...

<p>Various chemical properties can be used to characterise dissolving pulp. The quality of the pulp must be carefully controlled to ensure that it meets the requirements for its intended use and the further processes to be applied. If it is to be used to prepare viscose, or other cellulose derivatives, the key prop-erties of the pulp are its accessibility and reactivity. The studies described in this thesis investigated the potential utility of multivariate analysis of chemi-cal and spectral data for determining the properties of dissolving pulp. Dis-solving pulps produced by a two-stage sulfite process, both in the laboratory and a factory were produced pulps for this purpose. The analyses showed that pulp with high reactivity had short cellulose chains, low molecular weight, low polydispersity, low hemicellulose content, high content of ace-tone-extractable compounds, and high surface charge compared to pulp with low reactivity. Important chemical properties of the pulp, such as viscosity and alkali resistance, were successfully predicted from near infrared spectra. Predicting the reactivity, or the viscose filterability, of the pulp was more complex. Several chemical methods for analyzing the reactivity of the pulp were examined. The influence of the cellulose structure at the supermolecu-lar level on the reactivity of the pulp was explored by multivariate analysis of solid state 13C nuclear magnetic resonance spectra. Structural variables considered included: differences in hydrogen bonding, contents of hemicel-lulose, amorphous cellulose and crystalline cellulose I and II. Pulps with high reactivity have higher contents of cellulose I and amorphous cellulose than pulps with low reactivity, which have higher contents of cellulose II and hemicellulose.</p>

Various chemical properties can be used to characterise dissolving pulp. The quality of the pulp must be carefully controlled to ensure that it meets the requirements for its intended use and the further processes to be applied. If it is to be used to prepare viscose, or other cellulose derivatives, the key prop-erties of the pulp are its accessibility and reactivity. The studies described in this thesis investigated the potential utility of multivariate analysis of chemi-cal and spectral data for determining the properties of dissolving pulp. Dis-solving pulps produced by a two-stage sulfite process, both in the laboratory and a factory were produced pulps for this purpose. The analyses showed that pulp with high reactivity had short cellulose chains, low molecular weight, low polydispersity, low hemicellulose content, high content of ace-tone-extractable compounds, and high surface charge compared to pulp with low reactivity. Important chemical properties of the pulp, such as viscosity and alkali resistance, were successfully predicted from near infrared spectra. Predicting the reactivity, or the viscose filterability, of the pulp was more complex. Several chemical methods for analyzing the reactivity of the pulp were examined. The influence of the cellulose structure at the supermolecu-lar level on the reactivity of the pulp was explored by multivariate analysis of solid state 13C nuclear magnetic resonance spectra. Structural variables considered included: differences in hydrogen bonding, contents of hemicel-lulose, amorphous cellulose and crystalline cellulose I and II. Pulps with high reactivity have higher contents of cellulose I and amorphous cellulose than pulps with low reactivity, which have higher contents of cellulose II and hemicellulose.

Title: The Study of Dynamic Behaviour and Interactions During the Tempera- ture-Induced Phase Separation in Polymer Solutions Author: Hana Kouřilová Department / Institute: Charles University in Prague, Faculty of Mathemat- ics and Physics, Department of Macromolecular Physics Supervisor of the doctoral thesis: doc. RNDr. Lenka Hanyková, Dr. Abstract: 1 H and 13 C high-resolution NMR spectroscopies were used for the phase separation investigation in three types of polymer solutions: i) poly(N -isopropylmethacrylamide)/D2O/ethanol with or without negatively charged comonomer sodium methacrylate, ii) random copolymers poly(N -isopro- pylmethacrylamide-co-acrylamide) in D2O, D2O/ethanol and D2O/acetone and iii) D2O solutions of polymer mixtures poly(N -isopropylmethacrylamide)/poly(N - vinylcaprolactam). For i) cononsolvency effect and influence of temperature on the phase separation was studied. Differences between mesoglobules formed as a consequence of cononsolvency effect and of temperature were found. While inside the cononsolvency-induced mesoglobules no bound ethanol molecules were detect- ed, in the mesoglobules formed by the effect of temperature ethanol molecules were present. The charge introduced into the polymer chains strenghtens polymer- solvent interactions. For ii) mesoglobules were found to be...

Submitted by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2015-02-19T13:34:45Z No. of bitstreams: 5 gui.pdf: 4235660 bytes, checksum: a4da31a1b3421bf1fd546fc015611c65 (MD5) license_url: 52 bytes, checksum: 3d480ae6c91e310daba2020f8787d6f9 (MD5) license_text: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) license.txt: 2110 bytes, checksum: b4c884761e4c6c296ab2179d378436d4 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2015-02-20T10:39:27Z (GMT) No. of bitstreams: 5 gui.pdf: 4235660 bytes, checksum: a4da31a1b3421bf1fd546fc015611c65 (MD5) license_url: 52 bytes, checksum: 3d480ae6c91e310daba2020f8787d6f9 (MD5) license_text: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) license.txt: 2110 bytes, checksum: b4c884761e4c6c296ab2179d378436d4 (MD5) / Made available in DSpace on 2015-02-20T10:39:27Z (GMT). No. of bitstreams: 5 gui.pdf: 4235660 bytes, checksum: a4da31a1b3421bf1fd546fc015611c65 (MD5) license_url: 52 bytes, checksum: 3d480ae6c91e310daba2020f8787d6f9 (MD5) license_text: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) license.txt: 2110 bytes, checksum: b4c884761e4c6c296ab2179d378436d4 (MD5) Previous issue date: 2013-12-17 / Realizou-se a s?ntese de doadores e receptores glicos?dicos in?ditos que foram utilizados numa s?ntese convergente de um precursor da adenofostina A. Igualmente, a converg?ncia das sintonas tinha como prop?sito principal o estudo de rea??es de glicosila??o, ou seja, foram explorados dois m?todos de forma??o de liga??es glicos?dicas: o m?todo do tricloroacetoimidato e o m?todo de isomeriza??o do doador glicos?dico al?lico. A prepara??o dos aceptores e doadores glicos?dicos envolveu sequ?ncias de prote??o e desprote??o de grupos hidroxila a partir da adenosina e da D-glicose, respectivamente, privilegiando-se a forma??o de doadores armados e a observa??o da estereoqu?mica no carbono anom?rico. Os an?meros ? e ? formados nesta sequ?ncia de s?ntese foram separados, mas somente os an?meros ? foram motivo de caracteriza??o pelos m?todos de an?lise usuais de espectrometria RMN 1D e 2D, de massas e no infravermelho. Dessa forma, foram sintetizados dois aceptores glicos?dicos (17) e (18) e cinco doadores glicos?dicos (9), (11?), (11?), (13?) e (13?), sendo todas as subst?ncias in?ditas. Dentre os ensaios de glicosila??o somente o m?todo do tricloroacetoimidato produziu o produto desejado (glicosila??o entre 11? e 17) cuja caracteriza??o estrutural encontra-se em andamento. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2012. / ABSTRACT This works discusses the synton?s synthesis of the, unpublished glycosidic donors and aceptors that have been used in a convergent synthesis of a precursor of adenophostin A. Furthermore, the convergence of syntons main purpose was to study the glycosylation, ie been explored two methods of forming glycosidic linkages, the method of trichloroacetimidate and method of isomerization of the allyl glycoside donor. The preparation of donors and acceptors glycosidic sequences involving protection and deprotection of hydroxyl groups from adenosine and D-glucose, respectively, favoring the formation of armed donors and observation of stereochemistry at anomeric carbon. The and anomers formed in this synthesis sequence were separated, but the only reason anomers were characterization by usual methods of analysis of 1D and 2D NMR spectroscopy, mass and infrared. Thus, we synthesized two glycoside acceptors (17) and (18) and five donor glycoside (9), (11), (11), (13) and (13), all substances are novel. Among the glycosylation assays only the method of tricloroacetimidate gave the desired product (glycosylation between 11 and 17) that is the object of characterizing and whose data has not yet been completed and conclusive.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Changes in land use can take into soil chemical and physical quality degradation. In the hillside areas of the Rio Grande do Sul State (RS) land degradation vulnerability is elevated, due to the combination of a strong undulated to mountainous relief and shallow soils. The general purpose of this study was to evaluate the chemical and physical attributes of soils located in the Sul-riograndense Plateau Border under different land uses. Two representative sites of the Plateau Border, characterized by steep slope areas with prevalence of family farms, were selected (Silveira Martins county (SM) and São João do Polêsine county (SJ)), and also a transition area situated between the Plateau Border and the Medium Plateau (Júlio de Castilhos county (JC)). In SM soil samples were collected in areas of no-tillage (PD), tillage (PC), reforestation (RF) and native forest (MN). In SJ soil samples were collected under native forest (MN), secondary forest (MS), old cropping (LV), new cropping (LN) and abandoned cropping (LA) areas. In JC the samples were collected under native forest (MN), native prairie (CN) and no-tillage (PD) areas. Samples were collected from 0 to 10cm and from 10 to 20cm. Modifications were observed in soil chemical and physical attributes due to the different land uses when compared to the native forest. In systems that do not receive constant external additions, a decrease in soil chemical fertility was observed. Soil organic matter content decreased as the land use intensity increased. C-O-alquyl was the carbon group that presented the largest contribution in the spectra of 13C NMR, independent of the land use system. The main physical alterations observed were the decreases of soil macroporosity, total porosity and saturated hydraulic conductivity and the increase in soil density when compared to soil natural conditions. Soil aggregation parameters did not show to be good indexes to identify changes due to the land use in this study. / As mudanças na utilização das terras podem levar à degradação da qualidade química e física do solo. Nas áreas de encosta do estado do Rio Grande do Sul (RS) a vulnerabilidade à degradação das terras é elevada, devido a combinação de relevo forte ondulado a montanhoso e solos com pequena profundidade efetiva. O objetivo geral deste trabalho foi avaliar as características químicas e físicas do solo de áreas situadas no Rebordo do Planalto na região central do RS, sob diferentes usos da terra. Para isso foram selecionadas duas áreas representativas da região denominada Rebordo do Planalto, caracterizada por áreas de encosta com predomínio da agricultura familiar em pequena escala (Silveira Martins (SM) e São João do Polêsine (SJ)) e uma área de transição entre o Rebordo do Planalto e o Planalto Médio (Júlio de Castilhos (JC)). Em SM foram coletadas amostras de solo no sistema de plantio direto (PD), plantio convencional (PC), reflorestamento (RF) e mata nativa (MN). Em SJ foram coletadas amostras de solo sob os usos na mata nativa (MN), mata secundária (MS), lavoura velha (LV), lavoura nova (LN) e lavoura abandonada (LA). Em JC as amostras foram coletadas em áreas de mata nativa (MN), campo nativo (CN) e plantio direto (PD). As amostras foram coletadas na profundidade de 0-10 e 10-20 cm. Através dos resultados obtidos, observaram-se modificações nas características químicas e físicas do solo em função dos diferentes usos da terra, ao comparar com a mata nativa. Em sistemas que não recebem adições constantes de fontes externas, ocorreu uma depressão da fertilidade química. A matéria orgânica do solo teve diminuição nos teores, conforme aumentou a intensidade de uso da terra. O grupo C-O-alquil foi o grupo de carbono que apresentou a maior contribuição nos espectros de RMN 13C, independente do sistema de uso da terra. As principais alterações físicas ocorridas em comparação com as condições naturais do solo, foram diminuições da macroporosidade, porosidade total e condutividade hidráulica saturada e aumento na densidade do solo. Os parâmetros de agregação do solo, neste trabalho, não se mostraram como bons índices de avaliação para identificar mudanças em função dos diferentes usos da terra.

The work presented in this thesis has two parts. The first part deals with methodological developments in the area of solid-state NMR, relevant to the study of partially ordered systems. Liquid crystals are best examples of such partially ordered systems and they are easily oriented by the magnetic field used for the NMR study. They provide spectra rich in information useful for the study of structure and dynamic s of the oriented molecule. Dipolar couplings and anisotropic chemical shifts are relatively easy to obtain for these systems. However, the methodologies used for extracting the required information are constantly undergoing change, with newer ideas being used for optimal use of the technique and increasing the sensitivity of the methodology. In this thesis, existing methods used for obtaining dipolar couplings from oriented liquid crystalline samples are examined in detail and conditions for optimal use of the methods are investigated. Different approaches for enhancing the sensitivity of the techniques are also proposed. Estimation of chemical shift anisotropy of carbons for a molecule that is used as a building block for several mesogens has been obtained and its utility for estimating the order parameters of the system have been examined. The second part of the thesis deals with the application of solid state NMR methods to the study of a number of novel liquid crystalline systems and for the estimation of dynamics, order and orientation of the mesogenic molecules in the magnetic field. Chapter-2 deals with a detailed and systematic study to improve the sensitivity of cross-polarization based separated local field (SLF) NMR spectroscopy techniques such as PISEMA(Polarization Inversion Spin Exchange at the Magic Angle) and PDLF(Pro-ton Detected Local Field). The chapter has been further divided into three sections. Section-A describes the optimization procedure for cross-polarization period for reducing zero-frequency peaks in SLF experiments. Polarization Inversion(PI) is one of the important components of PISEMA and plays a crucial role in enhancing the dipolar cross-peaks and suppressing the axial-peaks. Shortening this period has the advantage of less r.f. power input into the system, thus less susceptibility to sample heating. Therefore it is crucial to arrive at the optimum condition for which maximum sensitivity and resolution are obtained. A detailed experimental investigation of the role of the initial po1arization period has been carried out for two different samples of static oriented liquid crystalline material at two different temperatures and a contact time of 2ms has been found to be optimal for such samples. Insection-B of this chapter, the initial preparation period of the experiment is considered as a possible means of increasing the sensitivity of the experiment. Thus the use of cross-polarization via the dipolar bath by the use of a diabatic demagnetization in the rotating frame(ADRF-CP) has been proposed to be incorporated into PISEMA. To understand the CP dynamics, magnetization in double-and zero-quantum reservoirs of an ensemble of spin-1/2 nuclei and their role in determining the sensitivity the experiments have been theoretically examined. Experimentally, a modification incorporating ADRF-CP is shown to result in enhancement of signal-to-noise by as much as 90% in the case of rigid single crystals of a model peptide and up to 50% in non-rigid, partially ordered liquid crystalline systems. In section-C another useful SLF technique known as PDLF spectroscopy has also been examined. In this case a sweep of one of the r.f. amplitudes(RAMP-CP),rather than ADRF is found to work well. The reason for the different behaviours has been discussed. Chapter-3 highlights two experimental approaches used to extract the chemical shift anisotropy(CSA) tensor information from rotating solids. Section-A is devoted to the measurement of the CSA values of thiophene by using MAS side band analysis, by extracting the principal values from the intensities of just a few spinning side bands. Experiments have been performed on thiophene-2 carboxylic acid and thiophene-3 carboxylic acid samples and the carbon CSA values have been obtained. In section-B, CSA values of carbons of the core unit of the liquid crystal4- hexyloxybenzoic acid (HBA) have been obtained by using the recoupling pulse sequence SUPER(Separation of Undistorted Powder patterns by Effortless Recoupling).HBA belongs to an important class of thermotropic liquid crystals which are structurally simple and often used as starting materials for many novel mesogens. As this molecule could serve as an ideal model compound, high resolution13C NMR studies of HBA in solution, solid and liquid crystalline phases have been also undertaken. The CSA values obtained from the 2D SUPER experiment showed good agreement to those computed by DFT calculations. The CSA values were used for obtaining the order parameter of the system at different temperatures. These matched well the order parameter obtained from the 13C-1 H dipolar couplings in the nematic phase determined by SLF spectroscopy at various temperatures. A knowledge of the CSA of the carbons is thus very useful, as they can be used for gaining knowledge about the system from the chemical shifts obtained from a simple 1D spectrum. In chapter-4, 1-and 2-dimensional13CNMR techniques have been utilized to obtain extensive information about some novel mesogenic molecules. Four molecules of different structure and topology have been taken up for study. These molecules have the following features. Mesogen-1 has a terminal hydroxyl group. Such systems with further modification can result in mesogenic monomers for side chain liquid crystalline polymers. Mesogen-2 has a dimethyl amino group at one end and has three phenyl groups connected by appropriate linking units that form the core. In the third case, mesogen-3, the terminal hydroxyl group of mesogen-1 is replaced with a hydrogen such that13C-1 H dipolar couplings provide directly information on molecular ordering and orientation. In the fourth case, mesogen-4, the core is built with four phenyl rings. Here the fourth ring is linked to other three rings via a flexible chain unit. In each of these cases the 2DSLFNMR experiments have been carried out where13C-1 H dipolar couplings as well as13C chemical shifts were used for obtaining the order parameters of various segments of the molecule. The data provide useful insight into the phase behaviour, ordering and orientation of the molecules. Chapter-5 discusses the applications of the natural abundance 13CNMR techniques to thiophene based mesogens, that have the potential for use in molecular electronics material. Typically, these molecules consist of phenyl rings appropriately connected by linking units with thiophene. Different core units as well as different linking units to thiophene have been considered. The six mesogens thus obtained have been investigated in detail using 1D and 2D NMR methods.13C-1 H dipolar couplings have been used to obtain ordering information, that show interesting correlation to the molecular orientation and dynamics.

The main aim of doctoral thesis is the study on physicochemical properties of humic substances (HS) by modern instrumental techniques. The subject of the study were HS isolated from South Moravian lignite, South Bohemian peat, forest soil Humic Podzol and finally extract from brown sea algae Ascophyllum nodosum. With respect on determination of structure and reactivity of these unique “biocolloids”, standard samples (Leonardite HA, Elliott Soil HS and Pahokee Peat HS) were also studied. These samples were obtained from International Humic Substances Society (IHSS). All mentioned substances were characterized by elemental analysis (EA), molecular absorption spectroscopy in ultraviolet and visible region (UV/Vis), infrared spectroscopy with Fourier transformation (FTIR), nuclear magnetic resonance spectroscopy of carbon isotope 13C (LS 13C NMR), steady-state and time resolved fluorescence spectroscopy. Obtained fluorescence, UV/Vis and 13C NMR spectra were used for calculation of fluorescence and absorption indexes, values of specific absorbance and structural parameters respectively, which were used for fundamental characterization of these “biocolloidal” compounds. Infrared spectroscopy with Fourier transformation was utilized for the identification of functional groups and structural units of HS. Evaluation of infrared spectra is quiet complicated by overlapping of absorption bands especially in fingerprint region. This problem was overcome by Fourier self-deconvolution (FSD). Steady-state fluorescence spectroscopy was used for deeper characterization of HS with respect to origin, structural units, amount of substituents with electron-donor and electron-acceptor effects, content of reactive functional groups, “molecular” heterogeneity, the degree of humification, etc. Parameters of complexation of samples Elliott Soil with heavy metal ions (Cu2+, Pb2+ and Hg2+) were obtained by using modified Stern-Volmer equation. These ions were chosen purposefully, because the interaction of HS with these ions is one of the fundamental criteria for the assessment of the reactivity of HS. Key part of the whole doctoral thesis is time-resolved fluorescence spectroscopy. It is able to determine the origin of emission of HS by method Time-Resolved Area Normalized Emission Spectra (TRANES). The viscosity of micro medium about excited fluorophores of HS was determined by Time-Resolved Emission Spectra (TRES).

<p>  </p> <p>Organic synthesis is the application of one or more reactions to the preparation of a particular target molecule, and can pertain to a single-step transformation or to a number of sequential chemical steps depicted by a scheme overall. The selection of a reaction or series of reactions while considering chemo-, regio-, and stereoselectivities in addition to protecting group strategies & redox manipulations highlights the complexity in designing & executing a synthetic plan while making a judgement about what is the most effective and efficient plan to synthesize any given chemical compound among numerous available options. To this end, chemical synthesis is the unifying theme of this thesis & was utilized and strategically applied to construct increasingly complex and diverse molecular architectures. </p> <p>Being the precise science that organic chemistry is, this discipline extends into many areas such as technology, biology & medicine, and even into the fine arts since it fosters unparalleled creativity and imagination in its practice. Research foci in chemical synthesis can encompass both the discovery and development of powerful reactions and the invention of strategies for the construction of defined target molecules, natural or man-made, more or less complex. Studies in the former area, synthetic methodology, fuel and enable studies in the latter area, target molecule and total synthesis campaigns, where the latter area offers a testing ground for the former. Consequently, the bulk of this research work is in organic methodology and will be covered in greater depth during chapters 2 and 3 where strategies, optimizations, & analyses are elaborated upon in light of searching & navigating the vast body of chemical literature in an effort to broaden and strengthen one's laboratory expertise as a synthetic chemist. Lastly, chapter 4 focuses not on traditional synthesis but on organic structure analysis relying on various techniques such as nuclear magnetic resonance (NMR), infrared (IR), ultraviolet-visible (UV-Vis) spectroscopy in combination with mass spectrometry (MS) and/or X-ray crystallography to hypothesize and confirm established structures, specifically phenolic oligomers. An ability to use spectroscopic data to evaluate organic structures by combining practical experience with fundamental knowledge will serve as a hallmark skill in one’s ability to problem-solve as an organic chemist.</p>