The thesis entitled “Controlling Stereochemistry at the Quaternary Center Using Bifunctional (Thio)urea Catalysis” is divided into five chapters. Chapter 1: Catalytic Enantioselective Construction of Quaternary Stereocenters through Direct Vinylogous Michael Addition of Deconjugated Butenolides to Nitroolefins The direct use of deconjugated butenolides in asymmetric C–C bond forming reaction is a powerful but challenging task because of the additional problem of regioselectivity along with the issues of diastereo- and enantioselectivity. In this chapter, a direct asymmetric vinylogous Michael addition of deconjugated butenolides to nitroolefins has been demonstrated for the construction of quaternary stereocenter at the γ-position of butenolides. A novel thiourea-based bifunctional organocatalyst, containing two elements of chirality, was synthesized starting from commercially available quinine and (S)-tert-leucine. Remarkably, the sense of stereoinduction in this process is dominated by the tert-leucine segment of the catalyst. Synthetically versatile & highly functionalized γ-butenolides with contiguous quaternary and tertiary stereocenters were synthesized stereoselectively. The reaction was found to be general and a wide range of nitroolefins, with both electron-rich and electron-deficient substituents, underwent smooth reaction under these mild conditions. Similarly, deconjugated butenolides, having various substituents at the γ-position were well tolerated under these reaction conditions and the products were obtained in excellent yields and with uniformly high diastereo- and enantioselectivities. Reference: Manna, M. S.; Kumar, V.; Mukherjee, S. Chem. Commun. 2012, 48, 5193–5195. Chapter 2: Catalytic Asymmetric Direct Vinylogous Michael Addition of Deconjugated Butenolides to Maleimides for the Construction of Quaternary Stereogenic Center In this chapter, a mild and operationally simple protocol for the direct vinylogous Michael addition of deconjugated butenolides to maleimides has been illustrated. Using bifunctional tertiary amino thiourea organocatalyst, derived from a ‘matched’ combination of trans-(1R,2R)-diaminocyclohexane (DACH) and (S)-tert-leucine, the Michael adducts were obtained in excellent yields and with good to high diastereoselectivities and outstanding enantioselectivities. Application of the corresponding diastereomeric catalyst indicated the dominance of the ‘DACH’ unit over the chiral side chain in determining the sense of stereoinduction. The practicality of this protocol is illustrated by substantial low catalyst loading (down to 5 mol%) and one-pot catalyst recycling. Based on the X-ray structure of the catalyst and observed stereochemistry of the Michael adduct, a stereochemical model is proposed which was further supported by additional experiment. Reference: Manna, M. S.; Mukherjee, S. Chem.–Eur. J. 2012, 18, 15277–15282. Chapter 3: Enantioselective Desymmetrization of Cyclopentenedione through Direct Catalytic Vinylogous Michael Addition of Deconjugated Butenolides Five-membered carbocycles containing one or more stereogenic centers on the ring are privileged structural motifs found in many biologically active natural and non-natural compounds. Among various methods for accessing these enantioenriched carbocyclic frameworks, desymmetrization of prochiral or meso-compounds through catalytic enantioselective transformations represents a powerful strategy. The biggest advantage of such asymmetric desymmetrization reactions lies in their ability in controlling stereochemistry remote from the reaction site. This chapter deals with a highly efficient desymmetrization protocol for 2,2-disubstituted cyclopentene-1,3-diones via direct vinylogous nucleophilic addition of deconjugated butenolides with the help of a tertiary amino thiourea bifunctional catalyst. In contrast to the existing desymmetrization protocols, this method represents a unique example where quaternary stereocenter is generated not only within the ring but also outside the cyclopentane ring. Densely functionalized products are obtained in excellent yields and with outstanding diastereo- and enantioselectivities. The robustness screening indicated that the reaction is highly tolerant to a variety of competing electrophiles and nucleophiles. The remarkable influence of the secondary catalyst site on the enantioselectivity points towards an intriguing mechanistic scenario. To the best of our knowledge, this is the first time such an effect is observed in the context of asymmetric catalysis. Reference: (1) Manna, M. S.; Mukherjee, S. Chem. Sci. 2014, 5, 1627–1633. (2) Manna, M. S.; Mukherjee, S. Org. Biomol. Chem. 2015, 13, 18–24. (Perspective) Chapter 4: Enantioselective Desymmetrization of Cyclopentenediones through Organocatalytic C(sp2)–H Alkylation Organic compounds are characterized by the presence of various C–H bonds. Functionalization of a specific C–H bond in a molecule with a selected atom or group are among the most straightforward and desirable synthetic transformations in organic chemistry. In this chapter, a simple protocol for the direct alkylation of olefinic C(sp2)–H bond has been developed, not only enantioselectively using an organocatalyst but more importantly without using any directing group. This alkylative desymmetrization of prochiral 2,2-disubstituted cyclopentene-1,3-diones is catalyzed by a dihydroquinine-based bifunctional urea derivative. Using easily accessible, inexpensive and air-stable nitroalkanes as the alkylating agent, this C(sp2)−H alkylation represents a near-ideal desymmetrization and delivers products containing an all-carbon quaternary stereogenic center in good to excellent yields and with high enantioselectivities. The mild reaction conditions allow for the introduction of various functionalized alkyl groups. The possibility of a second alkylation and its applications has also been demonstrated. This protocol is the first example of the use of nitroalkane as the alkyl source in an enantioselective transformation. It is expected that, these findings would have broader consequences and applications to other alkylative and related transformations. Reference: Manna, M. S.; Mukherjee, S. J. Am. Chem. Soc. 2015, 137, 130–133. (Highlighted in Synform 2015, 67–70) Chapter 5: Enantioselective Desymmetrization of Cyclopentenediones through Organocatalytic Formal C(sp2)–H Vinylation The development of catalytic enantioselective C(sp2)–H vinylation reactions remained relatively underexplored for a long time because of various challenges associated with it. As C(sp2)–H functionalization reactions do not generate any stereocenter at the reaction site, development of enantioselective C(sp2)−H functionalization must rely on desymmetrization of prochiral or meso-substrates. More important issue is the identification of a suitable directing group which can efficiently control the regioselectivity during the activation of C(sp2)−H bond. In this chapter, an efficient formal C(sp2)−H vinylation of prochiral 2,2-disubstituted cyclopentene-1,3-dione is developed without using any directing group. This formal C(sp2)−H vinylation of 2,2-disubstituted cyclopentene-1,3-dione is realized using a two-step operation: catalytic enantioselective Michael addition of deconjugated butenolides followed by a base mediated decarboxylation. The vinylated products, containing a remote all-carbon quaternary stereogenic center, are obtained in good yields and with good to high enantioselectivities. Synthetic utility of this protocol is demonstrated by converting the resulting chiral electron-deficient diene into various important building blocks. Significant erosion in enantioselectivity during the decarboxylation process was explained by a plausible mechanism, which was further supported by control experiments. Reference: Manna, M. S.; Sarkar, R.; Mukherjee, S. manuscript under preparation.

Polyurethane and the analogous ‘polyurethane-urea’ are high performance polymeric materials having remarkable properties such as high stiffness, abrasion and tear strengths. In many studies, the low strength rubbers have been blended with various types of polyurethanes for new and improved materials. However, until now, the reported heterogeneous blends offer only a narrow temperature range of application due to the high temperature softening of their polyurethane (-urea) phase. In addition, the conventional solution-or melt-blending methods are time and energy intensive, which tend to forfeit the economical realization of the reported blends. In contrast to earlier studies, a simplified reactive blending process is suggested to synthesize polyurethane-urea via a prepolymer route during blending with rubbers to obtain novel elastomeric materials having extended performance characteristics. The reactive blending process is opted to prepare blends based on nitrile butadiene rubber (NBR) and in-situ synthesized polyurethane-urea (PUU). The blending is carried out in an internal mixer at a preset temperature of 100°C. The critical temperatures of the reactive blending process are determined from the chemo-rheological analysis of a premix, composed of a 4,4′-diphenylmethane diisocyanate (MDI)/polyether (PTMEG) based prepolymer admixed with 1,3-phenylene diamine (mPD). The prepared NBR/PUU blends exhibit highly improved mechanical properties. Contrary to previous reports, the reinforced dynamic-mechanical responses of the novel blends remain stable till very high temperatures (≥180°C). The influence of diamine type on the in-situ synthesized polyurethane-urea and the performance of prepared blends are investigated. Four different diamines, namely 1,3-Phenylene diamine, 1,4-Bis(aminomethyl)benzene, 4,4′-Methylene-bis(2-chloroaniline) and 4,4ʹ-(1,3-Phenylenediisopropylidene)bisaniline, are selected to chain extend the prepolymer to PUU during blending with NBR. The chemical and domain structure of the PUUs are found to greatly influence the reinforced tensile and dynamic-mechanical responses of the NBR/PUU 70/30 blends. The PUU (based on MDI/PTMEG prepolymer and mPD) is blended with polar (CR, XNBR) and nonpolar (NR, EPDM, sSBR) rubbers. PUU compatibilizes with all the rubbers irrespective of their polarity and reinforces their tensile and dynamic-mechanical characteristics. The use of blends in industrial applications, for example, in a truck tire tread compound and as a roller covering material, is examined. In a simplified tire tread formulation, the carbon black for NR-CB composite is partially replaced with an equivalent quantity of PUU for NR/PUU-CB composite of similar hardness. The dynamic mechanical investigations reveal that the energy dissipation and strain dependent softening is high in NR-CB as compared to the NR/PUU-CB composite. In another application, NBR/PUU blend is successfully tested as a rubber roller covering material. The tested blend-covered roller retains its structural integrity and develops less heat build-up as compared to the silica filled NBR-covered roller. This shows a substantial suitability of the blend-covered rollers for film, printing and textile processing machinery. These novel blends are considered to be the promising new materials for many commercial applications including wheels, rubber rollers, belts or pump impellers.

Polyurethane and the analogous ‘polyurethane-urea’ are high performance polymeric materials having remarkable properties such as high stiffness, abrasion and tear strengths. In many studies, the low strength rubbers have been blended with various types of polyurethanes for new and improved materials. However, until now, the reported heterogeneous blends offer only a narrow temperature range of application due to the high temperature softening of their polyurethane (-urea) phase. In addition, the conventional solution-or melt-blending methods are time and energy intensive, which tend to forfeit the economical realization of the reported blends. In contrast to earlier studies, a simplified reactive blending process is suggested to synthesize polyurethane-urea via a prepolymer route during blending with rubbers to obtain novel elastomeric materials having extended performance characteristics. The reactive blending process is opted to prepare blends based on nitrile butadiene rubber (NBR) and in-situ synthesized polyurethane-urea (PUU). The blending is carried out in an internal mixer at a preset temperature of 100°C. The critical temperatures of the reactive blending process are determined from the chemo-rheological analysis of a premix, composed of a 4,4′-diphenylmethane diisocyanate (MDI)/polyether (PTMEG) based prepolymer admixed with 1,3-phenylene diamine (mPD). The prepared NBR/PUU blends exhibit highly improved mechanical properties. Contrary to previous reports, the reinforced dynamic-mechanical responses of the novel blends remain stable till very high temperatures (≥180°C). The influence of diamine type on the in-situ synthesized polyurethane-urea and the performance of prepared blends are investigated. Four different diamines, namely 1,3-Phenylene diamine, 1,4-Bis(aminomethyl)benzene, 4,4′-Methylene-bis(2-chloroaniline) and 4,4ʹ-(1,3-Phenylenediisopropylidene)bisaniline, are selected to chain extend the prepolymer to PUU during blending with NBR. The chemical and domain structure of the PUUs are found to greatly influence the reinforced tensile and dynamic-mechanical responses of the NBR/PUU 70/30 blends. The PUU (based on MDI/PTMEG prepolymer and mPD) is blended with polar (CR, XNBR) and nonpolar (NR, EPDM, sSBR) rubbers. PUU compatibilizes with all the rubbers irrespective of their polarity and reinforces their tensile and dynamic-mechanical characteristics. The use of blends in industrial applications, for example, in a truck tire tread compound and as a roller covering material, is examined. In a simplified tire tread formulation, the carbon black for NR-CB composite is partially replaced with an equivalent quantity of PUU for NR/PUU-CB composite of similar hardness. The dynamic mechanical investigations reveal that the energy dissipation and strain dependent softening is high in NR-CB as compared to the NR/PUU-CB composite. In another application, NBR/PUU blend is successfully tested as a rubber roller covering material. The tested blend-covered roller retains its structural integrity and develops less heat build-up as compared to the silica filled NBR-covered roller. This shows a substantial suitability of the blend-covered rollers for film, printing and textile processing machinery. These novel blends are considered to be the promising new materials for many commercial applications including wheels, rubber rollers, belts or pump impellers.

Av samtliga globala processer som reglerar jordsystemet är de biogeokemiska flödena av kväve (N) och fosfor (P) mest påverkade av mänskliga aktiviteter. Inerta former av N och P omvandlas till reaktiva former som sprids i miljön, där de orsakar eutrofiering och påverkar marina ekosystem negativt. Majoriteten av de reaktiva N- och P-formerna används för framställningen av mineralgödsel. Ett alternativt sätt att producera gödsel är att återvinna näringsämnena i avloppet. En teknik som återvinner näringsämnen i urin är basisk urintorkning. Teknologin stabiliserar urea med ett basiskt torkningsmedium och koncentrerar näringsämnena genom att evaporera vattnet i urinen. Slutprodukten är ett torrt gödsel i pulverform. I det här projektet testades urintorkningsteknologin för första gången i ett fältförsök. Ett system för urintorkning med kapacitet att förånga 40 kg urin dygn-1 m-2 konstruerades och integrerades i ett befintligt torrt sanitetssystem för användning under en period på tre månader. I projektet utvärderades 13 dygn av de 3 månaderna. Resultaten visade att 24 kg urin tillfördes systemet och att systemet kunde upprätthålla en kontinuerlig torkning av urinen. Efter torkningen återvanns majoriteten (97 %) av N i slutprodukten. På grund av att den tillförda mängden urin var liten blev växtnäringshalterna i slutprodukten och i torrsubstansen (TS) av slutprodukten låga. Systemet hade emellertid potential att torka mycket större kvantiteter urin. Om systemets fulla potential hade använts, det vill säga att torka 40 kg urin dygn-1 m-2, så hade särskilt N- och P-halterna ökat avsevärt. N-halterna hade även ökat ytterligare om torkningen hade utförts vid en lägre temperatur. Systemets energiförbrukning var hög, eftersom systemet hade en kontinuerlig energikonsumtion och även komponenter med hög effekt. I jämförelse med den konventionella avloppsvattenreningen och produktionen av mineralgödsel har systemet en hög energikonsumtion, men i jämförelse med en förbränningstoalett är systemets energiförbrukning likvärdig. För att minska energiförbrukningen kunde reglertekniska åtgärder utföras så att systemets energitillförsel upphör när systemet inte används. Systemets energiförbrukning får även ställas i relation till de problem som dagens system för livsmedelsproduktion och sanitet medför. Till skillnad från nämnda system möjliggör urintorkningsteknologin besparing av dricksvattenresurser, ett slutet kretslopp av näringsämnen och en minskad påverkan på miljön. / Of all global processes that regulate the earth system, the biogeochemical flows ofnitrogen (N) and phosphorus (P) are the most affected by human activities. Inert forms of N and P are converted into reactive forms that are dispersed in the environment, causing eutrophication and affecting marine ecosystems. The majority of the reactive N and P are used for the production of mineral fertilizers. An alternative way of producing fertilizers is to recycle nutrients from waste water. A technology that reuses nutrients in urine is alkaline urine drying. The technology stabilizes urea with an alkaline drying medium and concentrates the nutrients by evaporating the water in urine. The end-product is a dry fertilizer in powder form. In this master project, the alkaline urine drying technology was tested for the first time in field conditions. A system for urine drying with the capacity to evaporate 40 kg of urine day-1 m-2 was constructed and integrated into an existing dry sanitation system for use over a period of three months. The master project evaluated the system for 13 days of the 3 months. The results showed that 24 kg of urine was collected in the system, significantly less than what the system had been designed to dry. Furthermore, the results showed that the system functioned smoothly recovering 97 % of the urine-N in the end-product. The nutrient content in the end-product and the dry matter of the end-product was low due to the low amount of urine that was collected. However, the system had the potential to dry much larger quantities of urine. If the system would have been operated to function at full potential (drying 40 kg of urine day-1 m-2) the N- and P-content in the end-product would be much higher than that observed during the 13 days. Furthermore, the system if operated at lower temperatures has the potential to recover more N. The system’s energy consumption was high, as the system had a continuous energy consumption. In comparison with the conventional waste water treatment and the production of mineral fertilizers, the system has a high energy consumption, but compared to an incineration toilet, the system’s energy consumption is equivalent. In order to reduce the energy consumption, automatic control could be implemented so that the energy is switched off when the system is not used. The system’s energy consumption may also be set in relation to the problems that today’s systems for food production and sanitation entail. Unlike the aforementioned systems, the urine dehydration technology does not consume drinking water, it enables recycling of nutrients as well as a reduced impact on aquatic life.

Master of Science / Department of Chemistry / Mark Hollingsworth / The crystal structures of the inclusion compounds 1,6-diisocyanohexane/urea and 1,6-dicyanohexane/urea were refined at several temperatures from X-ray data. These urea inclusion compounds are commensurate structures with host:guest ratios of 6:1. In contrast with the ordinary helical topology of the urea host, these structures have stacked loop topologies of the host hydrogen bonds and crystallize in space group P21/n. At room temperature, both structures are distorted along [001] from hexagonal metric symmetry. As in earlier studies of 1-chloro-6-cyanohexane/urea, cooling 1,6-diisocyanohexane/urea gives rise to an exothermic phase transition (Hº = -856 cal mol 1, Sº = -5 cal mol-1 K-1) at 175 K that results in the cooperative translation of guest molecules by 5.5 Å along the channel axis. In the low temperature form, 1,6-diisocyanohexane/urea is distorted along [100], much like X(CH2)6Y, where X, Y = Br, Cl. Although the crystal structure of 1,6-dicyanohexane/urea is essentially isomorphous with that of the high temperature form of 1,6-diisocyanohexane/urea, it does not undergo an equivalent phase transition at low temperatures. Both of these systems exhibit dynamic disorder between two gauche conformers of the guest, which have mean planes of the alkyl chains lying within 1º of [100] (major conformer) and approximately 14º from [001] (minor conformer). The temperature dependence of site occupancy factors for the disordered sites yielded enthalpy differences between major and minor sites in 1,6-diisocyanohexane/urea and 1,6-dicyanohexane/urea of 216 and 127 cal mol 1, respectively. Since the low temperature form of 1,6-diisocyanohexane/urea is distorted along [100], this is favored at low temperatures by an increased concentration of the major conformer, which predominates in 1,6-dibromohexane/urea and congeners. In 1,6-diisocyanohexane/urea, the phase transition to the low temperature form occurs at a threshold concentration for the major conformer of 67%. With its shallower temperature dependence, 1,6-dicyanohexane/urea should not reach this threshold population until approximately 92 K, at which temperature the system cannot overcome the barrier for cooperative translation of guests along the channel axis.

Thesis (PhD (Chemistry and Polymer Science)--University of Stellenbosch, 2009. / The work presented in this dissertation describes the development of self-healing coatings based on thiol-ene chemistry. The approach was to synthesize capsules with thiol and ene compounds separately encapsulated. These capsules were embedded in various coating formulations and upon the formation of a crack with a razor blade, these capsules ruptured. This caused the healing agent to flow into the crack via capillary action and the thiol-ene healing mechanism was initiated. This resulted in recovery of the damaged coating and provided continued protection to the substrate. Pentaerythritol tetrakis(3-mercaptopropionate) (TetraThiol), 1,6-hexanediol diacrylate (DiAcrylate) and 1,6-hexanediol di-(endo, exo-norborn-2-ene-5-carboxylate) (DiNorbornene) are the thiol and ene compounds used in this study. Kinetic experiments indicated that both TetraThiol-DiAcrylate and TetraThiol-DiNorbornene monomer pairs undergo rapid polymerization and form a network within minutes upon exposure to UV radiation and with the addition of a photoinitiator. The TetraThiol-DiNorbornene monomer pair also showed a high rate of polymerization without the addition of a photoinitiator and/or exposure to UV radiation. Styrene-maleic anhydride (SMA) copolymers and chain-extended block copolymers with styrene (P[(Sty-alt-MAh)-b-Sty]) were synthesized via Reversible Addition-Fragmentation chain Transfer (RAFT)- mediated polymerization. These copolymers were used as surfactant in miniemulsification for the synthesis of core-shell particles with TetraThiol as the core material. It appeared that P[(Sty-alt-MAh)-b-Sty] block copolymers, sterically stabilized via the addition of formaldehyde, provide optimal stability to the core-shell particles. DiNorbornene is encapsulated via miniemulsion homopolymerization of styrene and well-defined, stable nanocapsules were obtained. TetraThiol and DiAcrylate microcapsules were synthesized via in-situ polymerization of urea and formaldehyde. Microcapsules with a particle size of one to ten micrometers and with a very smooth surface were obtained. These microcapsules and nanocapsules were embedded in poly(methyl acrylate) (PMA), styrene-acrylate and pure acrylic films and the self-healing ability of these coatings, after introduction of a crack with a razor blade, was assessed.

The initiation, persistence, and termination of harmful algal blooms (HABs) can all be influenced by nutrient availability. Recent studies have highlighted the role of both organic and inorganic nitrogen sources in HAB dynamics. The pelagophyte Aureoumbra lagunensis causes ecosystem disruptive algal blooms and is responsible for the longest recorded harmful algal bloom (1989-1997). Because of Aureoumbra's small size and its inability to use nitrate, it has been hypothesized that its ability to use ammonium and organic nitrogen, especially at low concentrations, contributed to the unusual persistence of this bloom. This project aimed to assess the response of Aureoumbra to inorganic and organic nitrogen sources by examining the expression of genes responsible for nitrogen assimilation, with an eventual intent of developing expression assays that are indicative of nitrogen source use and/or sufficiency in Aureoumbra. Large volume batch cultures of Aureoumbra were grown with either ammonium or urea as a nitrogen source. Physiological characteristics (C:N, chlorophyll [alpha] cell⁻¹, and Fv/Fm) were monitored throughout the growth period, and the expression of the AMT-1, AMT-2 and UREC genes was assayed at early-, mid- and late-exponential phases. The results show that Aureoumbra can use both ammonium and urea, and that it is well adapted to low-nutrient environments. Only one gene, AMT-1, appeared to be transcriptionally regulated in response to changing nitrogen concentration, and only to ammonium. The results of this study contribute to our understanding of how algae in general cope with low nutrient availability and should ultimately help to define the dynamics of these HAB events. / text

The objective of this research was to investigate the effects of slow release urea on N metabolism in cattle. The ruminal behavior of Optigen®II and the effect of basal diet on the in situ degradability of urea and Optigen®II were evaluated. The effect of slow release urea and its interaction with degradable intake protein (DIP) level in the diet on N retention and excretion was evaluated utilizing 8 Holstein steers in a 4 x 4 Latin square experiment. In addition, the effect of slow release urea and DIP level on ruminal and systemic urea kinetics was evaluated using stable isotope techniques with 8 Holstein steers in a 4 x 4 Latin square experiment. Finally, slow release urea was evaluated under a practical beef production setting. The performance of slow release urea was compared to regular feed grade urea in a 42 day receiving study (288 Angus cross steers) as well as a 70 day growing study (240 Angus cross steers). High forage diets increased the ruminal degradation rate of both urea and slow release urea an increased the extent of degradation of slow release urea when compared to high concentrate diets. Lower DIP concentrations in the diet reduced systemic urea production, ruminal ammonia and plasma urea concentrations and urinary urea excretion under most circumstances but also led to a reduction in N retention, reduced diet digestibility, lower feed intake, lower growth rate and decreased feed efficiency. High DIP intakes increased N retention, growth rate, diet digestibility and improved feed efficiency but also lead to increased excretion on urea N in the urine. Slow release urea improved N retention and efficiency of N retention in high DIP diets when compared to urea and generally reduced plasma urea and ruminal ammonia concentrations. Compared to urea, slow release urea did not significantly improve the production of receiving cattle. However Optigen®II improved the feed efficiency when compared to urea on high concentrate diets but reduced feed efficiency on high forage diets.

The analysis of pharmacotherapy by patients suffering with DM in Greece I Author: Georgios Kalaitzidis Tutor: Professor RNDr.Jiri Vlcek,CSc. Department of Social and Clinical Pharmacy, Charles University in Prague, Faculty of Pharmacy in Hradec Kralove. Introduction: The diabetes in developed countries concerns 11% of people over 70 years and is the cause of 3% of total deaths in general population. Aim: The aim of the study was to assess the Pharmacotherapy of Diabetes mellitus type II in a pharmacy of a small town of Greece, Veria. Methods: It is retrospective cross-sectional study, which was conducted in a pharmacy in a small town of Greece, Veria. The study population consists of 60 patients with known Type II diabetes Melitus. The data collection was performed by a self-reported questionnaire, which was created and developed by the researcher and filled by the respondents. Results: The mean age of the sample was 56.5±17.5 years. Most of them were females (n=40). Most of the patients knew their fasting glucose level (93.3%,n=56).Of the patients who knew their fasting glucose level, 36 (64.3%) patients had high fasting glucose level and 20 (35.7%) had physiological fasting glucose level. From all the patients(n=60), some of them visited their physician every 6 months (n=24), and every 3 months...

A cana-de-açúcar é uma importante alternativa na suplementação de ruminantes no período de menor disponibilidade de forragem. A sua ensilagem permite a armazenagem por longos períodos, além de apresentar benefícios logísticos. Entretanto, as altas concentrações de etanol encontradas nas silagens sem aditivos podem reduzir o consumo voluntário e, conseqüentemente afetar o desempenho animal. Dois experimentos foram realizados para avaliar os efeitos do uso da cana-deaçúcar fresca e ensilada com aditivos sobre o desempenho da lactação de cabras e a digestibilidade aparente das dietas para borregos. Exp. I: Trinta e seis cabras da raça Saanen (15&#177;3 dias de lactação) foram utilizadas para avaliar os efeitos do fornecimento de rações contendo silagem de cana-de-açúcar sobre o consumo de matéria seca, os parâmetros sangüíneos, o comportamento ingestivo e a produção e composição do leite. As cabras foram alojadas individualmente, por 12 semanas, em baias do tipo ?tie stall?. Exp. II: Doze borregos Santa Inês foram mantidos em gaiolas para ensaio de metabolismo para a determinação da digestibilidade aparente das rações experimentais. As dietas foram compostas de 50% de volumoso e 50% de concentrado, constituindo os quatro tratamentos experimentais: a) cana-de-açúcar fresca (CC), b) silagem de cana-de-açúcar inoculada com L. buchneri (5x104 ufc/g MV) (SAD), c) silagem de cana-de-açúcar aditivada com 1,0% de uréia (U1,0) e d) silagem de canade- açúcar aditivada com 1,5% de uréia (U1,5). O delineamento experimental dos experimentos foi o de blocos completos casualizados. O consumo de matéria seca, a variação no peso corporal, a produção e composição do leite foram semelhantes (P>0,05) nas comparações CC vs SAD e U1,0 vs U1,5. O tratamento CC comparado ao SAD apresentou aumento (P<0,05) na concentração de glicose sangüínea (GS), no nitrogênio uréico plasmático (NUP), no tempo de ingestão e mastigação nas 24 horas e no tempo de ruminação e mastigação nas 6 primeiras horas após o fornecimento das rações. A concentração de uréia no leite foi maior (P<0,05) para o tratamento U1,0 quando comparado ao tratamento U1,5. As silagens contendo uréia promoveram maior (P<0,05) teor de gordura, sólidos totais e uréia no leite, e menores GS e NUP quando comparadas a CC. O coeficiente de digestibilidade aparente da FDN foi maior (P<0,05) para as silagens quando comparadas à cana-de-açúcar fresca. A digestibilidade aparente da PB foi maior para o tratamento U1,0 quando contrastado com o U1,5. A inoculação microbiana propicionou resultados semelhantes de produção e composição do leite. O uso de aditivos na silagem de cana-de-açúcar aumenta a digestibilidade da FDN. / Sugar cane is an important roughage source for ruminants. Sugar cane silage is an alternative feed which may improve operation efficiency at farm level. However, high levels of ethanol found in sugar cane ensiled without additive may reduce voluntary feed intake and may affect animal performance. Two experiments were performed to evaluate the effects of using fresh sugar cane and sugar cane silage treated with microbial (Lactobacillus buchneri) or chemical (urea) additives on lactation performance of goats and diets digestibility in ram lambs. Trial 1: Thirty-six lactating Saanen does (15&#177;3 DIM) were used to evaluate the effects of feeding sugar cane silage treated with microbial or chemical additives on dry matter intake, blood parameters, ingestive behavior and milk yield and milk composition. Goats were assigned to a complete randomized block design (according to milk production, DIM and number of lactation) and housed individually in a tie stall during 12 weeks. Trial 2: Twelve Santa Inês ram lambs were placed in metabolic crates to evaluate diet digestibility. Experimental diets were composed by 50:50 (concentrate: roughage ratio) TMR. Experimental treatments were the roughage source: fresh sugar cane (FSC), sugar cane silage with L. buchneri (SCS + Lb), 5x104 cfu/g wet basis, sugar cane silage with 1% urea wet basis (SCS1%) or sugar cane silage with 1.5% urea wet basis (SCS1.5%). Dry matter intake, body weight variation, milk yield and composition were similar (P>0.05) among treatments (FSC vs SCS + Lb and SCS1% vs SCS1.5%). Treatment FSC compared to SCS+Lb showed higher (P<0.05) blood glucose concentration (BG), plasma urea nitrogen (PUN), time spent eating and chewing in 24 hours, time spent ruminating and chewing at initial 6 hours. Milk urea nitrogen was higher (P<0.05) for SCS1% compared to SCS1.5%. Silages added with urea showed higher (P<0.05) milk fat, milk total solids, milk urea, and lower (P<0.05) BG and PUN when compared to the FSC treatment. NDF digestibility was lower (P<0.05) for SCS compared to sugar cane silages (FSC vs SCS + Lb; FSC vs SCS1% and SCS1.5%). CP digestibility was higher (P<0.05) for animals fed SCS1.0% compared those fed SCS1.5%. There were no differences (P>0.05) on nitrogen balance in all comparison evaluated. Microbial inoculants had no detrimental effect, showing similar results for milk production and composition. The use of additives in sugar cane silage improves NDF digestibility.