Synthesis, Secondary Structure, and Anion Binding of Acyclic Carbohydrate-Derived Oligo(amide-triazole)s

A family of linear, carbohydrate-derived oligo(amide-triazole)s has been designed and synthesized. These molecules possess a regular distribution of triazole rings (from one to four) linking the carbohydrate units to give dimer to pentamer derivatives. Their binding to halide anions was qualitatively analyzed by means of NMR spectroscopy and mass spectrometry. All the compounds were able to bind chloride anions, with a stoichiometry that depended on the chain length. The dimer and trimer gave 2:1 host/chloride ratio, while the tetramer and pentamer gave 1:1 complexes. The secondary structure of the oligo(amide-triazole)s was studied using NMR spectroscopy and circular dichroism. These studies showed that the larger host molecules (tetramer and pentamer) adopted a stabilized U-turn and were able to bind just one chloride anion. Only the pentamer displayed a helical conformation, which was slightly distorted in the presence of chloride salts. Interestingly, chloride binding involves not only the triazole-CH but also H atoms from the carbohydrate moieties. These compounds could be applied for chloride sensing by ESI-MS.Fil: Fidalgo, Daniela Marina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Monge, Maria Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; ArgentinaFil: Varela, Oscar Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Kolender, Adriana Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentin

When Statutory Regimes Collide:Will Wisconsin Right to Life and Citizens United Invalidate Federal Tax Regulation of Campaign Activity?

In Federal Election Commission v. Wisconsin Right to Life (2007) and Citizens United v. Federal Elections Commission (2010), the United States Supreme Court dramatically reduced the ability of Congress to regulate campaign finance activities of corporations and others active in elections. Many of the same activities are still subject to restrictions by the Internal Revenue Code, which regulates the type and amount of political campaign activities that certain nonprofits exempt under federal tax law can engage in. In the wake of the campaign finance decisions, the constitutionality of the tax law’s restrictions on campaign activity is now being challenged in the lower courts. This Article analyzes the two recent campaign finance decisions and campaign finance precedents more broadly to determine how, if at all, the Roberts’ Court’s campaign finance jurisprudence is likely to alter existing tax law jurisprudence in the area of campaign activity. It finds that, for the most part, tax law constitutional doctrines have developed independently of other areas of First Amendment free speech law. Based upon an analysis of the distinctive tax law doctrines, the Article concludes that the tax law provision prohibiting section 501(c)(3) charities from engaging in campaigns is likely to withstand challenges arguing that the provision prevents these nonprofits from engaging in protected political speech. However, there is some likelihood that the tax law prohibition is vulnerable to constitutional attack under traditional doctrines of vagueness or overbreadth due to the lack of precision of the terms of the political prohibition, as these have been elaborated by the IRS and the courts to date

Antiviral Activities of Sulfated Polysaccharides Isolated from Sphaerococcus coronopifolius (Rhodophytha, Gigartinales) and Boergeseniella thuyoides (Rhodophyta, Ceramiales)

Water-soluble sulfated polysaccharides isolated from two red algae Sphaerococcus coronopifolius (Gigartinales, Sphaerococcaceae) and Boergeseniella thuyoides (Ceramiales, Rhodomelaceae) collected on the coast of Morocco inhibited in vitro replication of the Human Immunodeficiency Virus (HIV) at 12.5 μg/mL. In addition, polysaccharides were capable of inhibiting the in vitro replication of Herpes simplex virus type 1 (HSV-1) on Vero cells values of EC50 of 4.1 and 17.2 μg/mL, respectively. The adsorption step of HSV-1 to the host cell seems to be the specific target for polysaccharide action. While for HIV-1, these results suggest a direct inhibitory effect on HIV-1 replication by controlling the appearance of the new generations of virus and potential virucidal effect. The polysaccharides from S. coronopifolius (PSC) and B. thuyoides (PBT) were composed of galactose, 3,6-anhydrogalactose, uronics acids, sulfate in ratios of 33.1, 11.0, 7.7 and 24.0% (w/w) and 25.4, 16.0, 3.2, 7.6% (w/w), respectively

Monoclonal antibodies directed to fucoidan preparations from brown algae

Cell walls of the brown algae contain a diverse range of polysaccharides with useful bioactivities. The precise structures of the sulfated fucan/fucoidan group of polysaccharides and their roles in generating cell wall architectures and cell properties are not known in detail. Four rat monoclonal antibodies, BAM1 to BAM4, directed to sulfated fucan preparations, have been generated and used to dissect the heterogeneity of brown algal cell wall polysaccharides. BAM1 and BAM4, respectively, bind to a non-sulfated epitope and a sulfated epitope present in the sulfated fucan preparations. BAM2 and BAM3 identified additional distinct epitopes present in the fucoidan preparations. All four epitopes, not yet fully characterised, occur widely within the major brown algal taxonomic groups and show divergent distribution patterns in tissues. The analysis of cell wall extractions and fluorescence imaging reveal differences in the occurrence of the BAM1 to BAM4 epitopes in various tissues of Fucus vesiculosus. In Ectocarpus subulatus, a species closely related to the brown algal model Ectocarpus siliculosus, the BAM4 sulfated epitope was modulated in relation to salinity levels. This new set of monoclonal antibodies will be useful for the dissection of the highly complex and yet poorly resolved sulfated polysaccharides in the brown algae in relation to their ecological and economic significance

Qualitaetssteigernde Massnahmen bei der Entwicklung von Software-Systemen im Bauwesen durch Objektrelationen

The present thesis shows that the interpretation of relationships between classes are of main importance for solving civil engineering problems in object-oriented information systems. In particular, the quality of an application is influenced by the implementation of relationships where the quality of an application can be described by general criteria like reusability, extensibility, maintainability, etc. Two fundamentally different implementationtypes can be distinguished: Internal integration of relationships in the participating classes versus modeling relationships externally as independent classes. Both possibilities are analysed with regard to the above mentioned quality criteria. It is shown that the external implementation of all relationships decisively increases the quality of an application. It is therefore sensible to model relationships using classes as efficiently as possible. These classes can then be collected to create a specific class library. Examples in the domain of civil engineering given in the thesis show how these relationship classes can guarantee efficient and well-structured application developments. (orig.)SIGLEAvailable from TIB Hannover: RA 3043(97-4) / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekDeutsche Forschungsgemeinschaft (DFG), Bonn (Germany)DEGerman

Mythical structures, family and identity in contemporary mainstream animated cinema

Praca poświęcona jest analizie specyficznej konwencji fabularnej wypracowanej w kinie animowanym głównego nurtu na przestrzeni pierwszych dwóch dekad XXI wieku. Opiera się ona na konflikcie między jednostką (dorastającym protagonistą) a zbiorowością (ze szczególnym uwzględnieniem rodziny). Autor podejmuje próbę definicji "kina animowanego głównego nurtu" jako osobnego zjawiska we współczesnej kinematografii poprzez jego uwarunkowania produkcyjne i technologiczne, a także przynależność do meta-gatunkowej kategorii "filmu familijnego". Opisany i zanalizowany zostaje wpływ koncepcji struktur mitycznych na konstrukcję fabuł omawianych filmów. Następnie przedstawiona zostaje refleksja na temat różnych strategii obrazowania relacji rodzinnych w kinie animowanym głównego nurtu oraz ich związek z procesami konstruowania i negocjowania indywidualnej oraz zbiorowej tożsamości.The paper analyses a specific plot pattern developed in the mainstream animated cinema during the first two decades of the 21st century. This pattern is based on the conflict between an individual (an adolescent protagonist) and a collective (with particular emphasis on family). The author attempts to define "mainstream animated cinema" as a separate phenomenon in contemporary cinematography, through its production and technological conditions, as well as it’s connection to the meta-genre category of “family film”. The influence of the concept of mythical structures on the construction of the films' plots' is described and examined. An analysis of how the family relationships are presented in discussed films and how do they connect to the processes of constructing and negotiating individual and collective identity is provided

The elements of gonzo strategy in american documentary film in years 2001 - 2009

Praca bada zasadność stosowania określenia "gonzo dokument" w odniesieniu do twórczości takich reżyserów jak Michael Moore, Morgan Spurlock i Yes Meni. Filmy tych twórców przeanalizowane zostają pod kątem wykorzystania strategii charakterystycznych dla Nowego Dziennikarstwa: subiektywizacji i fabularyzacji. Analizie poddana zostaje również ideologia zawarta w tych utworach.The paper examines the use of a term "gonzo documentary" to describe works of such directors as Michael Moore, Morgan Spurlock and The Yes Men. Movies directed by these filmmakers are being analyzed to show the use of strategies characteristic for New Journalism: subjective perspective and elements of fiction. The paper consists also an analysis of ideology that is present in these movies

Polysaccharides from Nothogenia fastigiata y Georgiella confluens (Rhodophyta) : new analytical methods for algal polysaccharides

Este trabajo de Tesis versa sobre cuatro aspectos principales: l- Estudio de los polisacáridos del alga roja Nolhogenia jásligiala (Galaxauraceae, Nemaliales) y evaluación de su actividad antiviral. Comprende un sistema de D-mananos con uniones α-(l—>3), sulfatados en las posiciones 2 y 6, y con ramificaciones simples de D-xilosa enlazada β-(l—>2).Los xilomananos contenían mayoritariamente cationes de calcio y magnesio, que estaban involucrados en la formación de complejos entre los polisacáridos del sistema mediante interacciones cooperativas carbohidrato-carbohidrato dependientes de calcio. La fracción F6' fue la más activa frente a varias cepas de HSV tipos 1 y 2, dos de ellas resistentes a aciclovir. Por otra parte, no presentó actividad anticoagulante, lo cual constituye una ventaja para su aplicación potencial como agente antiviral en formulaciones de aplicación local. 2- Aplicación de espectrometría de masa UV-MALDI-TOF, para determinar los pesos moleculares y sus funciones de distribución, sobre xilomananos sulfatados y xilanos neutros de N.fastigiala. 3- Análisis estructural de los polisacáridos de Georgiella confluens (Ceramiaceae, Ceramiales). Los resultados indicaron la presencia de una cadena central de agarano altamente metilado con un esquema de sustitución inusual en galactanos de algas rojas: sulfatación en C-3 de unidades de α-L-galactosa y ramificaciones simples de xilosa en la posición 4 de β-D-galactosa. 4- Desarrollo de un método de desulfatación para polisacáridos sulfatados empleando clorotrimetilsilano. Permitió completar el análisis estructural de los xilogalactanos de G. confluens. También se encontraron las mejores condiciones para la desulfatación de carragenano kappa comercial, a fin de probar su eficacia en un polisacárido con máximo contenido de unidades de 3,6-anhidrogalactosa. El estudio por experimentos RMN mono- y bidimensionales de carragenano beta -obtenido por desulfatación de carragenano kappa permitió la asignación completa de su espectro protónico.This Thesis comprises four major sections: l- Analysis of the polysaccharides from the red seaweed Nolhogenia filsligiala (Galaxauraceae, Nernaliales) and evaluation of their antiviral activities. The sulfated polysaccharides extracted from this seaweed comprise a family of α-(l → 3)-linked D-mannans, 2- and 6-sulfated and having single stubs of β-(1 → 2)-linked D-xylose. The high content of calcium and magnesium cations revealed the complexation -mediated by calcium-dependent, cooperative carbohydrate-carbohydrate interactions- of polysaccharides belonging to the system. Fraction F6' proved to be the most active against several HSV strains, two of them resistant to acyclovír. At the same time, F6' did not exhibit anticoagulant properties, making it interesting for potential use as an antiviral agent in local formulations. 2- Application of UV-MALDI-TOF mass spectrometry to xylans and sulfated xylomannans in order to determine their molecular weights and distribution functions. 3- Structural analysis of the polysaccharides from Georgiella confluens (Ceramiaceae, Ceramiales). The results indicated the presence of a highly methylated agaran backbone with an unusual substitution pattern for red seaweed galactans: sulfation mainly at the 3-position of the α-L-galactose units and the presence of xylose single stubs at the 4-position of the β-D-galactose residues. 4- Development of a desulfation method for sulfated polysaccharides using chlorotrimethylsilane. Its application made possible the structural elucidation of the sulfated xylogalactans from G. confluens. Besides, in order to determine its efficiency in a polysaccharide with the highest 3,6-anhydrogalactose content, the best conditions for desulfation of commercial kappa carrageenan were tested. Complete assignment of the 1H NMR rcsonances of beta carrageenan -obtained by desulfation of kappa carrageenan- was achieved by means of mono- and bidimensional NMR techniques.Fil:Kolender, Adriana Andrea. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina

Synthesis and characterization of poly-O-methyl-[n]-polyurethane from a d-glucamine-based monomer

Aminoalditol 1-amino-1-deoxy-d-sorbitol (1) was readily converted into 2,3,4,5-tetra-O-methyl derivative 5, a key precursor of a sugar-based [n]-polyurethane. For the polymerization, the free amino or primary hydroxyl groups of 5 were selectively activated and employed as starting monomers in two alternative procedures. Thus, the amino function of 5 was converted into the isocyanate derivative by treatment with di-tert-butyltricarbonate, and polymerized in situ in the presence of Zr(IV) acetylacetonate. The resulting poly(1-amino-1-deoxy-2,3,4,5-tetra-O-methyl-d-sorbitol)urethane (8) had a moderate molecular weight and showed the presence of urea units. The alternative synthesis of 8 involved the activation of the free hydroxyl group of 5 as the corresponding phenylcarbonate. The polymerization of this α-amino-ω- phenylcarbonate alditol monomer does not require a metal catalyst. The resulting material exhibited an improved molecular weight and higher purity than that obtained via the isocyanate. [n]-polyurethane 8 was highly soluble in water as well as in common organic solvents (chloroform, acetone, ethyl acetate, etc) and was obtained as an amorphous material which was characterized thermally and spectroscopically.Fil: Kolender, Adriana Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Arce, Silvina M.. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Varela, Oscar Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentin