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Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/91222/1/1780360231_ftp.pd
Evaluation of an educational program for primary care practitioners, on the management of osteoarthritis
No Abstract.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/37772/1/1780280119_ftp.pd
Synthetic H-bonding information oligomers
The nucleic acids contain chemical information in the form of a sequence of bases. This information content is expressed through sequence selective duplex formation and template directed synthesis. To date, the only programmable artificial information molecules that can truly rival the nucleic acids, in terms of their function, are structurally very similar to the nucleic acids.
This thesis describes a synthetic approach to duplex forming hydrogen bonding oligomers that contain information in the form of a sequence of H-bond donor and acceptor groups, in the pursuit of a programmable material that is orthogonal to the nucleic acids.
Chapter 1 is a literature review of natural and synthetic information molecules and their applications in nanotechnology, including an overview of the structurally reengineered versions of the nucleic acids, foldamers, template polymerisation and synthetic duplexes. The review highlights the absence of totally synthetic information oligomers, that are orthogonal to the nucleic acids, and Chapter 2 sets out the aims of this thesis, which is to address this gap.
Chapter 3 describes the synthesis of oligomers equipped with phenol H-bond donors and phosphine oxide H-bond acceptors. Through cooperative H-bond formation, these oligomers form double stranded complexes, which were characterised by NMR titrations and thermal denaturation experiments. For each additional H-bond there is an order of magnitude increase in association constant.
In Chapter 4 it is demonstrated that the modular design for the oligomers in Chapter 3 represents a general strategy to synthetic information oligomers. Two new classes of H-bond acceptor oligomer were synthesised, bearing pyridine and pyridine N-oxide groups. Both these systems also exhibit cooperative duplex formation with H-bond donor oligomers, which were characterised by NMR titration.
Chapter 5 examines the ability of mixed sequence 3-mers formed of H-bond donors (phenol) and H-bond acceptors (pyridine N-oxide) to form duplexes in a sequence selective manner. All 8 combinations of donor and acceptor were synthesised, and NMR titrations were used to measure the association constants for each pairwise combination of oligomers. Sequence matched duplexes generally have the highest association constants, but there are some anomalies
Lebensweltliche Motive in der Lyrik Christine Bustas und Christine Lavants
Die vorliegende Arbeit beschäftigt sich mit der Lyrik Christine Lavants und Christine Bustas
in Hinblick auf deren lebensweltliche Motive. Schwerpunkt ist das lyrische Werk der 1950er
Jahre, wobei auch früher bzw. später entstandene Gedichte, Prosatexte sowie Briefe als Intertexte
zu Hilfe genommen werden. Die Auswahl umfasst vier Bereiche: Natur und florale Motive,
Nahrungsmittel, Hausrat und ähnliche Dinge und zu guter Letzt den menschlichen Körper.
Aus dem biologischen Bereich wird das Motiv der Distel einer genaueren Analyse unterzogen
– es ist kein Zufall, dass es sich bei den behandelten Texten meist um Blumengedichte
jenseits der Verklärung handelt. Nutzbares Kraut und Unkraut sind zeittypische Motive; letzteres
kann auch als Symbol der Subversion gelesen werden. Von den Nahrungsmotiven wird
Hauptaugenmerk auf jenes des Brotes gelegt, ist es doch in unserem Kulturkreis Hauptnahrungsmittel
und in mehrerlei Hinsicht symbolbehaftet. Das Brot wird untersucht als Leib
Christi, als Symbol der Tischgemeinschaft, hauptsächlich ist und bleibt es allerdings schlicht
eines: Essen für Hungrige. Aus den mannigfaltigen Motiven des Hausrats habe ich das Gefäß
gewählt – dieses ist als schlichter Gegenstand, als poetologisches Motiv (jenes der Form, die
einen Inhalt verschiedener Art fassen kann) sowie im Gender-Diskurs als Symbol fĂĽr den
Frauenleib lesbar. Der Körperdiskurs wird anhand des Herzmotivs, wohl dem häufigsten in
der deutschsprachigen Lyrik, veranschaulicht.
Viele Bedeutungen der Lyrik Bustas und vor allem Lavants sind sehr versteckt und erst nach
genauerem Hinsehen und Ausdeuten erkennbar. Die methodische Vorgehensweise orientiert
sich stark an den Texten. Die Biographien werden besonders dann relevant, wenn es um die
konkreten Lebenswelten der Dichterinnen geht. Oft erschlieĂźen sich allerdings radikalere Lesarten
von Gedichten, die ansonsten als brav gelten können, erst durch zusätzliches Wissen.
Daher erfolgen auch Auseinandersetzungen mit historischer, biologischer und medizinischer
Fachliteratur. Die beiden letzteren sind vor allem relevant, was Wortschöpfungen betrifft. Sozialgeschichtliche
Bezüge sind in vielerlei Hinsicht von Bedeutung: Sie bieten ein zusätzliches
Verständnis, wie sich die Verteilung von gesellschaftlichem Reichtum, religiöse Anschauungen
und Strukturen oder die Rolle von Frauen in den Texten widerspiegelt. Auch zeitgenössische
Intertexte und literaturgeschichtliche BezĂĽge spielen eine Rolle. Die Analyse geschieht
hauptsächlich auf Wortebene, da diese bei beiden aussagekräftiger und individueller
ist als formale Kriterien wie Reim und Metrum, die meist recht konventionell gehalten sind.
Das Bild von Lavant und Busta, die oft als religiöse Schriftstellerinnen rezipiert werden, ist um zahlreiche Facetten erweiterbar. Das Miteinbeziehen gesellschaftlicher Problematik und
die Beschäftigung mit dem Zusammenspiel von Sprache und Inhalt, bei dem es oft zu Reibungen
und BrĂĽchen kommt, sowie mit der eigenwilligen Metaphorik zeigen, dass den beiden ein
Platz in der literarischen Moderne zusteht.The present thesis deals with the poetry of Christine Lavant and Christine Busta focussing on
motifs of everyday life. The analysis deals mainly with the poems written in the 1950es, but
also includes earlier or later texts, prose and letters to show intertextual relations and to develop
a deeper understanding of the poems. The motifs selected for discussion come from four
different fields: Nature and floral motifs, food and nutrition, everyday goods and – last but not
least – the human body. From biology, I have chosen to focus on the motif of the thistle. It is
not a mere coincidence that the flower poems open spaces beyond idealization: Herbs and
weeds are typical motifs of the time, the latter can also be seen as a subversive symbol. The
main food motif is bread, since it is the most important element of nutrition in our culture and
has various connotations: It can be seen as the body of Christ or as a symbol of communal
meals, but its most important function is to feed the hungry. From the diverse motifs of everyday
objects the vessel will be analyzed in depth – it can be read as a mere object, as a poetological
metaphor (form, which can hold any kind of content) or, in gender discourse, as a symbol
for the female womb. The body discourse in Lavant’s and Busta’s poetry is illustrated by
an analysis of the heart motif, probably the most common one in poetry in German.
Many meanings in the poems of Busta and Lavant are hidden and can only be understood after
careful analysis. The method of my thesis is strongly text-based. The biographies become
relevant where the actual living situations of the poets are concerned. But sometimes poems
that at first glance might be considered affirmative reveal a more radical interpretation when
analyzed using specialist knowledge. Hence historical, biological and medical literature is discussed
as well. The last two of those are particularly useful to explain unusual word coinages.
Social history is important from many points of view: The historical facts supply a deeper understanding
of how the distribution of wealth, religious opinions and structures or the situation
of women appear in the texts. This also includes inter-texts written at the same time or earlier.
Linguistic analysis mainly happens on the level of words, which is definitely more relevant
for the work of Lavant and Busta than categories like meter or rhyme. Those normally
follow a quite conventional style. The image of Lavant and Busta, often seen as purely religious
writers, can be extended, bringing it closer to reality. Considering socio-political issues,
the interplay of language and content, which sometimes causes frictions and fractures, as well
as their characteristic use of metaphor, leads to the conclusion that both of them deserve their
place in literary modernism
Mix and match recognition modules for the formation of H-bonded duplexes.
Oligomeric molecules equipped with complementary H-bond recognition sites form stable duplexes in non-polar solvents. The use of a single H-bond between a good H-bond donor and a good H-bond acceptor as the recognition motif appended to a non-polar backbone leads to an architecture with interchangeable recognition alphabets. The interactions of three different families of H-bond acceptor oligomers (pyridine, pyridine N-oxide or phosphine oxide recognition module) with a family of H-bond donor oligomers (phenol recognition module) are compared. All three donor-acceptor combinations form stable duplexes, where the stability of the 1 : 1 complex increases with increasing numbers of recognition modules. The effective molarity for formation of intramolecular H-bonds that lead to zipping up of the duplex (EM) increases with decreasing flexibility of the recognition modules: 14 mM for the phosphine oxides which are connected to the backbone via a flexible linker; 40 mM for the pyridine N-oxides which have three fewer degrees of torsional freedom, and 80 mM for the pyridines where the geometry of the H-bond is more directional. However, the pyridine-phenol H-bond is an order of magnitude weaker than the other two types of H-bond, so overall the pyridine N-oxides form the most stable duplexes with the highest degree of cooperativity. The results show that it is possible to use different recognition motifs with the same duplex architecture, and this makes it possible to tune overall stabilities of the complexes by varying the components.We thank the EPSRC and ERC for fundin
NEUROPSYCHIATRIC FINDINGS IN PATIENTS EXPOSED TO POLYBROMINATED BIPHENYLS
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Sequence-Selective Formation of Synthetic H-Bonded Duplexes
Oligomers equipped with a sequence of phenol and pyridine N-oxide groups form duplexes via H-bonding interactions between these recognition units. Reductive amination chemistry was used to synthesize all possible 3-mer sequences: AAA, AAD, ADA, DAA, ADD, DAD, DDA, and DDD. Pairwise interactions between the oligomers were investigated using NMR titration and dilution experiments in toluene. The measured association constants vary by 3 orders of magnitude (102 to 105 M–1). Antiparallel sequence-complementary oligomers generally form more stable complexes than mismatched duplexes. Mismatched duplexes that have an excess of H-bond donors are stabilized by the interaction of two phenol donors with one pyridine N-oxide acceptor. Oligomers that have a H-bond donor and acceptor on the ends of the chain can fold to form intramolecular H-bonds in the free state. The 1,3-folding equilibrium competes with duplex formation and lowers the stability of duplexes involving these sequences. As a result, some of the mismatch duplexes are more stable than some of the sequence-complementary duplexes. However, the most stable mismatch duplexes contain DDD and compete with the most stable sequence-complementary duplex, AAA·DDD, so in mixtures that contain all eight sequences, sequence-complementary duplexes dominate. Even higher fidelity sequence selectivity can be achieved if alternating donor–acceptor sequences are avoided.We thank the Engineering and Physical Sciences Research Council (EP/J008044/2) and European Research Council (ERC-2012-AdG 320539-duplex) for funding
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