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  • Inorganic Chemistry  (83,665)
  • Organic Chemistry  (68,935)
  • Electronic books
  • ddc:080
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  • 1
    facet.materialart.
    Unknown
    Publication Date: 2019-10-24
    Keywords: ddc:080
    Language: German
    Type: annualzib , doc-type:report
    Format: application/pdf
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  • 2
    facet.materialart.
    Unknown
    Publication Date: 2019-10-24
    Keywords: ddc:080
    Language: German
    Type: annualzib , doc-type:report
    Format: application/pdf
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  • 3
    facet.materialart.
    Unknown
    Publication Date: 2019-10-24
    Keywords: ddc:080
    Language: German
    Type: annualzib , doc-type:report
    Format: application/pdf
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  • 4
    Publication Date: 2016-06-09
    Description: Im Rahmen dieser Arbeit wurde ein individuell anpassungsfähiges Modell entwickelt und implementiert, das die Perfusion in menschlichen soliden Tumoren beschreibt und für verschiedene Zeitpunkte w¨ahrend regionaler Hyperthermie ein lokal abhängiges Temperaturprofil berechnet. Da vor jeder Simulation alle wichtigen Parameter anhand von Ultraschall-, MRT- oder Angiogrammbildern individuell bestimmt werden können, wird eine patientenspezifische Aussage ¨uber das intratumorale Antwortverhalten bereits vor der eigentlichen Behandlung möglich. In Abh¨angigkeit von der Qualität der zur Verfügung stehenden anatomischen Daten über das zu simulierende Gebiet kann das Modell beliebig verfeinert oder bei Mangel an detaillierten Informationen auch mit Minimaldaten und reduzierter räumlicher Genauigkeit benutzt werden. Die für eine Simulation benötigten 2- oder 3- dimensionalen Geometrien können leicht mit der am ZIB entwickelten Software Amira erstellt und zur Berechnung in KARDOS, einem ebenfalls am ZIB implementierten Löser für nichtlineare partielle Differentialgleichungen, eingelesen werden. Mit Hilfe dieses Modells wird eine einfache, aber realistische und aussagekräftige Simulation für die Therapieplanung einer klinischen Hyperthermieanwendung ermöglicht, die innerhalb kurzer Zeit vorbereitet und durchgeführt werden kann.
    Keywords: ddc:080
    Language: German
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 5
    Publication Date: 2016-06-30
    Description: In dieser Arbeit werden effiziente Co-Reservierungs-Algorithmen vorgestellt, mit denen Rechenressourcen mehrerer Cluster im Grid reserviert werden können. Es werden fünf Algorithmen vorgestellt, die flexible Co-Reservierungsanfragen ermöglichen. In einer Co-Reservierungsanfrage müssen die angeforderten CPUs der Teilreservierungen exakt festgelegt werden. Die Cluster und die Startzeiten, bei denen die Teilreservierungen durchgeführt werden, ermittelt ein Co-Reservierungs-Algorithmus erst bei der Anfragebearbeitung. Die Benutzer können die Startzeit in der Anfrage eingrenzen, in dem sie eine früheste Startzeit und eine Deadline angeben. In den bisher entwickelten Reservierungsverfahren können Benutzer nur starre Co-Reservierungsanfragen stellen, in denen sie für alle Attribute der Teilreservierungen exakte Werte angeben müssen. Eine flexible Co-Reservierungsanfrage erlaubt einem Grid-Reservierungsdienst optimierte Reservierungsvarianten durchzuführen, da er aus vielen Reservierungsvarianten auswählen kann. Die Anwendungen von lokalen Benutzern können durch die Grid-Reservierungen verzögert werden. Bei der Auswahl der Reservierungsvarianten kann ein Grid-Reservierungsdienst dies berücksichtigen und den negativen Einfluß der Grid-Reservierungen verringern. Bei zwei Co-Reservierungs-Algorithmen werden auch zusätzliche Sortiervorgaben des Klienten bei der Auswahl der Reservierungsvarianten beachtet. Die Algorithmen wurden durch Simulationen mit dem Workload eines realen großen Supercomputers ausgewertet. Die Untersuchungen zeigen, daß sowohl die lokalen als auch die Grid-Benutzer von den flexiblen Anfragen profitieren können. Den lokalen Benutzern wurden die Ressourcen weniger oft durch zu früh gestellte Reservierungsanfragen entzogen. Die Grid- Benutzer können ihrerseits komfortabel eine optimierte Reservierungsvariante durchführen lassen.
    Keywords: ddc:080
    Language: German
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 6
    Publication Date: 2016-06-30
    Keywords: ddc:080
    Language: German
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
    Format: application/pdf
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  • 7
    Unknown
    Hershey, PA : Idea Group Pub
    Keywords: Electronic books ; Internet marketing
    Pages: 1 v. (various pagings)
    ISBN: 1-591-40826-1
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  • 8
    Keywords: Electronic books ; Electronic commerce, Management ; Information technology, Management ; Technological innovations, Management
    Pages: 1 v. (various pagings)
    ISBN: 1-591-40631-5
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  • 9
    Publication Date: 2020-08-05
    Keywords: ddc:080
    Language: English
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 10
    Publication Date: 2020-08-05
    Description: In dieser Diplomarbeit werden grundlegende Probleme der kostenoptimalen Dimensionierung von Telekommunikationsnetzwerken untersucht. Diese werden als lineare gemischt ganzzahlige Programme formuliert, wobei sich in der Modellierung auf die Konzepte Routing und Kapazitätszuweisung beschränkt wird. Es werden parallel drei übliche, aus der Praxis motivierte Möglichkeiten behandelt, die auf gerichteten oder ungerichteten Kanten eines Netzwerkes installierte Kapazität zu nutzen. Diese unterscheiden wir als DIrected, BIdirected und UNdirected. Die studierten Probleme treten als Relaxierungen vieler realistischer Fragestellungen der Netzwerkoptimierung auf. Sie enthalten elementare Strukturen, deren Studium ausschlaggebend ist für das Verständnis komplexerer Modelle. Letztere können zusätzliche Erfordernisse berücksichtigen, wie zum Beispiel die Ausfallsicherheit von Netzwerken. Zur Lösung solcher NP-schweren Optimierungsprobleme werden erfolgreich Branch & Bound und Schnittebenenverfahren kombiniert (Branch & Cut). Für die Wirksamkeit dieser Algorithmen ist es sehr nützlich, möglichst genaue Kenntnisse der Struktur der Seitenflächen der zugrundeliegenden Polyeder zu haben, welche die konvexe Hülle der Lösungsmenge beschreiben. Es sind starke gültige Ungleichungen zu finden, welche hochdimensionale Seitenflächen oder sogar Facetten definieren. Diese sollten zudem schnell separiert werden können und die numerische Stabilität der Algorithmen möglichst nicht beeinflussen. Diese Arbeit beschäftigt sich im Wesentlichen mit der sehr allgemeinen Rundungstechnik Mixed- Integer Rounding (MIR) zur Verstärkung gültiger Ungleichungen unter Verwendung der Ganzzahligkeitsnebenbedingungen. Es wird eine MIR-Prozedur motiviert, bestehend aus den Schritten Aggregieren, Substituieren, Komplementieren und Skalieren, welche durch Ausnutzung der Struktur der gegebenen Parameter zu einer gültigen Basisungleichung führt, die dann durch MIR eine starke und oft facetten-induzierende Ungleichung gibt. Es werden verschieden Klassen solcher Ungleichungen untersucht und auf ihre Praxistauglichkeit beim Einsatz in Branch & Cut-Verfahren getestet. Nach einer kurzen Einführung werden in Kapitel 2 die für uns in dieser Diplomarbeit relevanten Probleme definiert. Kapitel 3 gibt eine ausführliche Übersicht über die Technik MIR.Wir beschäftigen uns vor allen Dingen mit den Begriffen Superadditivität und Lifting und behandeln Aspekte wie Numerik und beschränkte Variablen. Kapitel 4 und Kapitel 5 umfassen Untersuchungen zu so genannten cut sets. Diese Polyeder werden durch Schnitte in Netzwerken definiert und relaxieren die von uns behandelten Probleme. Hauptsächlich durch MIR entwickeln wir sowohl neue als auch bekannte Klassen von facetten-definierenden Ungleichungen für cut sets, wobei strukturelle Unterschiede herausgearbeitet werden, die durch die drei verschiedenen Typen der Kapzitätsbereitstellung und durch beschränkte Variablen entstehen. Als ein zentrales Resultat wird bewiesen unter welchen Bedingungen facetten-induzierende Ungleichungen für cut sets auch Facetten der zugehörigen relaxierten Polyeder sind. Im Kapitel 6 geben wir weitere Typen von MIR-Ungleichungen an, die auf anderen Netzwerkstrukturen basieren und weisen ferner auf offene Fragen sowie interessante Ideen hin. Das Kapitel 7 widmet sich schließlich der Entwicklung und Implementation von Separationsalgorithmen. Wir testen einige der entwickelten Ungleichungsklassen mit Hinblick auf Ihre Wirksamkeit zur Lösung von realistischen Problemen der Netzwerkdimensionierung aus der Telekommunikation und diskutieren die Ergebnisse.
    Keywords: ddc:080
    Language: German
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 11
    Publication Date: 2016-06-30
    Description: Diese Arbeit dokumentiert den Entwurf und die Implementierung einer NFS-Schnittstelle zum ZIBDMS. Das ZIBDMS, welches derzeit am Zuse-Institut Berlin entwickelt wird, ist ein Managementsystem für verteilte Daten in heterogenen Umgebungen [10]. Es soll die einfache Benutzung von Mechanismen zur Replikation sowie neue Möglichkeiten des Zugriffs und der Verwaltung von Metadaten und Datenobjekten ermöglichen. Dem Nutzer bietet das System verschiedene Sichten: Neben der klassischen, hierarchischen Sicht mit Verzeichnissen und Dateien wird auch eine attributbasierte Zugriffsmethode angeboten, in der Datenobjekte ausschließlich über Attribut/Wert-Paare referenziert werden. Für den Benutzer transparent, soll sich das System im Hinblick auf die Verfügbarkeit von Daten und Metadaten selbsttätig optimieren. Um Skalierbarkeit gew¨ahrleisten zu können, werden intern Peer-to-Peer- Techniken entwickelt und benutzt. Die NFS-Schnittstelle erhöht die Nutzbarkeit des Systems, da Client- Implementierungen für nahezu alle Betriebssysteme zur Verfügung stehen. Der Benutzer kann so über das gewohnte Dateisystem Daten und Metadaten pflegen, ohne spezifisches Vorwissen zu benötigen. In dieser Arbeit wird untersucht, inwiefern sich die Semantik des ZIBDMS auf jene des NFS-Protokolls übertragen läßt. Weiterhin wird das Konzept von Pseudodateien beschrieben und diskutiert, inwiefern es eine brauchbare Lösung darstellt, den im Vergleich zur NFS-Semantik wesentlich größeren Funktionsumfang des ZIBDMS für den Anwender nutzbar zu machen. Pseudodateien sind nicht-persistente Objekte, welche für den Benutzer als reguläre Datei sichtbar werden und die erweiterte Funktionalitäten wie die Bearbeitung von Metadaten oder die Platzierung von Replikaten über die Dateisystem-Sicht des NFS zur Verfügung stellen sollen. Schließlich werden Leistungsmessungen an den benutzten Komponenten des ZIBDMS vorgenommen und vergleichbaren Systemen gegen übergestellt. Die Aufmerksamkeit liegt hier auf der zugrundeliegenden Katalog-Technologie sowie dem durch das NFS-Protokoll verursachten Overhead.
    Keywords: ddc:080
    Language: German
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 12
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    Cheltenham, UK ; Northampton, MA : Edward Elgar
    Keywords: Electronic books ; Environmental policy, Australia ; Industries, Case studies, Environmental aspects, Australia
    Pages: ix, 216 p.
    ISBN: 1-8454-2572-3
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  • 13
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    Cheltenham, U.K ; Northampton, Mass : Edward Elgar
    New horizons in international business  
    Keywords: Corporate governance ; Corporations, Growth ; Electronic books ; International business enterprises, Management ; International economic relations ; Investments, Foreign, Government policy
    Pages: 1 v. (various pagings)
    ISBN: 1-8454-2557-X
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  • 14
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    London ; Sterling, Va : Millward Brown/Kogan Page
    Keywords: Advertising, Psychological aspects ; Advertising, Research ; Electronic books ; Human information processing, Research
    Pages: xxiv, 232 p.
    ISBN: 1-423-71114-9
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  • 15
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    London ; Sterling, VA : Kogan Page
    Keywords: Business enterprises, Environmental aspects ; Business ethics ; Electronic books ; Factory and trade waste, Environmental aspects ; Industrial management ; Pollution prevention ; Small business, Environmental aspects ; Social responsibility of business
    Pages: xv, 485 p.
    ISBN: 1-423-70883-0
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  • 16
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    Cambridge, U.K ; New York, N.Y : Cambridge University Press
    Keywords: Cellular telephone services industry ; Electronic books ; Mobile communication systems, Economic aspects ; Wireless communication systems, Economic aspects
    Pages: 1 v. (various pagings)
    ISBN: 0-511-11564-4
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  • 17
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    Cambridge ; New York : Cambridge University Press
    Keywords: Shakespeare, William, Tragedies ; Electronic books ; Identity (Psychology) in literature ; Tragedy ; Violence in literature
    Pages: ix, 228 p.
    ISBN: 0-511-11352-8
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  • 18
    Keywords: Electronic books ; Finance ; Finance, History
    Pages: viii, 195 p.
    ISBN: 1-8454-2573-1
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  • 19
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    New York : Cambridge University Press
    Keywords: Capital market ; Electronic books ; Futures market ; Stock exchanges
    Pages: 1 v. (various pagings)
    ISBN: 0-511-11580-6
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  • 20
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    Abingdon : Helicon Pub
    Keywords: Art, Dictionaries ; Electronic books ; Signs and symbols, Dictionaries
    ISBN: 1-423-71132-7
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  • 21
    Keywords: Business enterprises, Computer networks ; Electronic books
    Notes: Who do you know? -- The seven keys to a powerful network -- Face-to-face vs. virtual communications -- Introduction to social software -- Email lists -- Relating in real-time -- Virtual communities -- Web logs (blogs) -- Social visibility software -- Virtual becoming reality -- The future of social software -- Netiquette -- Manage the email deluge -- The virtual you -- Privacy, safety, and other concerns -- Increase your character -- Increase your competence -- Build the relevance level of your network -- Build strong ties -- Increase the level and quality of information -- Grow the number of people in your network -- Increase the diversity of your network -- Ten simple steps to radically improve your network online -- Finding a job -- Marketing -- Sales -- Business development -- Volunteering
    Pages: 1 v. (various pagings)
    ISBN: 0-8144-2893-2
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  • 22
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    Cambridge ; New York : Cambridge University Press
    Keywords: Shakespeare, William, Language ; Shakespeare, William, Romeo and Juliet ; Shakespeare, William, Stage history, 1950- ; Shakespeare, William, Stage history, England, London ; Electronic books ; English language, Pronunciation, Early modern, 1500-1700 ; Globe Theatre (London, England : 1996- )
    Pages: xviii, 188 p.
    ISBN: 0-511-11364-1
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  • 23
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    Cambridge, U.K ; New York : Cambridge University Press
    Keywords: Electronic books ; Religion, Study and teaching (Higher) ; Theology, Study and teaching (Higher)
    Pages: xvii, 230 p.
    ISBN: 0-511-11355-2
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  • 24
    Unknown
    Northhampton, Mass : Edward Elgar Pub
    New horizons in international business  
    Keywords: Japan, Economic conditions, 1945- ; Japan, Economic policy, 1945- ; Electronic books ; Industries, Japan
    Pages: 1 v. (various pagings)
    ISBN: 1-8454-2567-7
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  • 25
    Keywords: Electronic books ; Motion pictures, Dictionaries
    ISBN: 1-423-71126-2
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  • 26
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    Ottawa : International Development Research Centre
    Keywords: Electronic books ; Electronic commerce, Case studies, Asia
    Notes: Action research on e-commerce for small artisans and development organizations : Pan-Asia E-commerce / Aniceto C. Orbeta, Jr -- Direct marketing of artisanal products through the Internet / Rajveer Singh -- E-marketers : an innovative approach to e-commerce / Loyola Joseph and Santosh Narayanan -- Impact of policy on development of e-commerce in Vietnam / Tran Ngoc Ca
    Pages: xi, 99 p.
    ISBN: 1-552-50179-5
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  • 27
    Unknown
    Cheltenham, U.K ; Northampton, Mass : Edward Elgar
    Keywords: European Union countries, Appropriations and expenditures ; Electronic books ; Finance, Public, Auditing, European Union countries ; Fiscal policy, European Union countries
    Pages: xvi, 256 p.
    ISBN: 1-8454-2560-X
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  • 28
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    Cambridge, UK ; New York : Cambridge University Press
    Keywords: Autonomy (Psychology) ; Electronic books ; Ethics, Modern
    Notes: Planning agency, autonomous agency / Michael E. Bratman -- Autonomy without free will / Bernard Berofsky -- Autonomy and the paradox of self-creation : infinite regresses, finite selves, and the limits of authenticity / Robert Noggle -- Agnostic autonomism revisited / Alfred R. Mele -- Feminist intuitions and the normative substance of autonomy / Paul Benson -- Autonomy and personal integration / Laura Waddell Ekstrom -- Responsibility, applied ethics, and complex autonomy theories / Nomy Arpaly -- Autonomy and free agency / Marina A.L. Oshana -- The relationship between autonomous and morally responsible agency / Michael McKenna -- Alternative possibilities, personal autonomy, and moral responsibility / Ishtiyaque Haji -- Freedom within reason / Susan Wolf -- Procedural autonomy and liberal legitimacy / John Christman -- The concept of autonomy in bioethics : an unwarranted fall from grace / Thomas May -- Who deserves autonomy, and whose autonomy deserves respect? / Tom L. Beauchamp -- Autonomy, diminished life, and the threshold for use / R.G. Frey
    Pages: ix, 350 p.
    ISBN: 0-511-08224-X
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  • 29
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    Palo Alto, CA : Stanford University Press
    Latin American development forum series  
    Keywords: Latin America, Economic conditions ; Economic stabilization, Latin America ; Electronic books ; Macroeconomics ; Structural adjustment (Economic policy), Latin America
    ISBN: 0-8213-5820-0
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  • 30
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    Cheltenham, U.K ; Northampton, Mass : Edward Elgar
    Keywords: Economic assistance, Developing countries ; Economic development ; Electronic books ; Public administration, Developing countries
    Pages: x, 190 p.
    ISBN: 1-8454-2552-9
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  • 31
    Keywords: Wolfensohn, James D. ; Economic development, Finance ; Electronic books ; World Bank
    Pages: viii, 156 p.
    ISBN: 0-8213-6174-0
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  • 32
    Keywords: Electronic books ; World Bank
    Pages: xix, 546 p.
    ISBN: 0-8213-6157-0
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  • 33
    Unknown
    Kalamazoo, Mich : W.E. Upjohn Institute for Employment Research
    Keywords: Electronic books ; Insurance, Unemployment ; Insurance, Unemployment, Cross-cultural studies
    Notes: Economic performance and unemployment -- Unemployment protection -- Unemployment compensation in the OECD-20 countries -- Unemployment compensation in the CEE-FSU countries -- Unemployment compensation in East and South Asia -- Unemployment compensation in Latin America and Caribbean countries -- Three problem areas for unemployment compensation programs -- Concluding remarks
    Pages: 1 v. (various pagings)
    ISBN: 1-417-59635-X
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  • 34
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    London ; Philadelphia : Jessica Kingsley Publishers
    Keywords: Child welfare, Research, Great Britain ; Children of minorities, Services for, Great Britain ; Electronic books ; Family social work, Great Britain ; Social work with minorities, Great Britain
    Pages: 255 p.
    ISBN: 1-423-71058-4
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  • 35
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    Cheltenham, U.K ; Northampton, Mass : Edward Elgar Pub
    Keywords: Electronic books ; Employee motivation, Europe ; Hours of labor, Flexible, Europe ; Incentives in industry, Europe ; Insurance, Unemployment, Europe ; Labor market, Europe ; Labor supply, Europe
    Pages: 1 v. (various pagings)
    ISBN: 1-8454-2562-6
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  • 36
    Unknown
    Cheltenham, U.K ; Northampton, Mass : Edward Elgar
    Keywords: Electronic books ; Euro area, Congresses ; Euro, Congresses ; International finance, Congresses ; Monetary policy, Congresses
    Pages: viii, 163 p.
    ISBN: 1-8454-2566-9
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  • 37
    Keywords: Business planning ; Conglomerate corporations, Management ; Conglomerate corporations, Planning ; Corporate culture ; Corporations, Growth ; Electronic books
    Notes: The challenge of new businesses -- Beating the odds -- The difficulties of building new legs -- When low growth is better than gambling -- The new business traffic lights -- Diversification -- Searching for new businesses -- Is there a role for corporate venturing? -- Positioning and supporting a new business -- An age of realism
    Pages: xv, 321 p.
    ISBN: 1-417-59769-0
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  • 38
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    New York, NY : Springer Science+Business Media
    Monographs in computer science  
    Keywords: Electronic books ; Object-oriented programming (Computer science) ; Reverse engineering
    Pages: xiv, 208 p.
    ISBN: 0-387-23803-4
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  • 39
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    Washington, D.C : World Bank
    Keywords: Bankruptcy, Congresses ; Consolidation and merger of corporations, Congresses ; Corporate reorganizations, Congresses ; Electronic books ; Financial crises, Congresses ; International finance, Congresses
    Pages: xlix, 382 p.
    ISBN: 0-8213-6225-9
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  • 40
    Unknown
    North Hampton, Mass : Edward Elgar
    Keywords: Capitalism, Moral and ethical aspects ; Democracy, Moral and ethical aspects ; Economics, Moral and ethical aspects ; Electronic books ; Social justice ; Social responsibility of business ; Social security, Moral and ethical aspects ; Welfare state, Moral and ethical aspects
    Pages: 1 v. (various pagings)
    ISBN: 1-8454-2570-7
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  • 41
    Unknown
    Northampton, Mass : Edward Elgar Pub
    Keywords: Electronic books ; Environmental economics ; Environmental policy ; Institutional economics
    Pages: 1 v. (various pagings)
    ISBN: 1-8454-2574-X
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  • 42
    Keywords: United States, History, Dictionaries ; Electronic books
    Pages: xi, 608 p.
    Edition: 2nd ed., updated and expanded
    ISBN: 1-417-59441-1
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  • 43
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    Austin : University of Texas Press
    Keywords: Acropolis (Athens, Greece) ; Athena (Greek deity), Cult ; Electronic books ; Inscriptions, Greek ; Kore statues ; Polychromy, Greece, Athens ; Votive offerings, Greece, Athens
    Pages: xiv, 230 p., [32] p. of plates
    Edition: 1st ed
    ISBN: 0-292-79763-X
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  • 44
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    Oxford ; New York : Oxford University Press
    Keywords: Electronic books ; Vision disorders ; Visual perception
    Pages: ix, 135 p.
    ISBN: 1-423-70567-X
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  • 45
    Keywords: Electronic books ; Evaluation research (Social action programs) ; Human services, Research, Methodology ; Social service, Research, Methodology
    Notes: The process of using social research -- Some key issues in appraising social research -- Questionnaire design for quantitative research: structured instruments -- Surveys and sampling -- Experimental and quasi-experimental designs -- The qualitative interview -- Ethnography and practice -- Content analysis: grounded theory -- Qualitative evaluation -- Multimethod research
    Pages: 256 p.
    ISBN: 1-423-71051-7
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  • 46
    Keywords: Electronic books ; Hispanic Americans, Case studies, Social conditions ; Human geography, Case studies, United States
    Notes: Hispanic American legacy, Latino American diaspora / Daniel D. Arreola -- The plaza in Las Vegas, New Mexico: a community gathering place / Jeffrey S. Smith -- Social geography of Laredo, Texas, neighborhoods: distinctiveness and diversity in a majority-Hispanic place / Michael S. Yoder and Renée La Perrière de Gutiérrez -- Barrio under siege: Latino sense of place in San Francisco, California / Brain J. Godfrey -- Globalization of the barrio: transformation of the Latino cultural landscapes of San Diego, California / Lawrence A. Herzog -- Barrio space and place in southeast Los Angeles, California / James R. Curtis -- Changing Latinzation of New York City / Inés M. Miyares -- Soccer and Latino cultural space: metropolitan Washington fútbol leagues / Marie Price and Courtney Whitworth -- The cultural landscape of a Puerto Rican neighborhood in Cleveland, Ohio / Albert Benedict and Robert B. Kent -- Latinos in polynucleated Kansas City / Steven L. Driever -- Se venden aqu:̓ Latino commercial landscapes in Phoenix, Arizona / Alex Oberle -- Hispanics in the American South and the transformation of the poultry industry / William Kandel and Emilio A. Parrado -- Hispanization of Hereford, Texas / Terrence W. Haverluk
    Pages: viii, 334 p.
    Edition: 1st ed
    ISBN: 0-292-79744-3
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  • 47
    Unknown
    Cheltenham, UK ; Northampton, MA : Edward Elgar
    Keywords: Capital movements ; Debts, External ; Electronic books ; Finance, Developing countries ; Foreign exchange ; International finance ; Monetary policy ; Monetary policy, Developing countries
    Pages: 1 v. (various pagings)
    ISBN: 1-8454-2469-7
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  • 48
    Unknown
    Leiden ; Boston : Brill
    International studies in sociology and social anthropology  
    Keywords: Weber, Max ; Electronic books ; Rationalism ; Sociology, History ; Sociology, Philosophy
    Pages: xlvii, 376 p.
    ISBN: 1-423-71239-0
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  • 49
    Publication Date: 2020-08-05
    Keywords: ddc:080
    Language: English
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 50
    Publication Date: 2020-08-05
    Description: This diploma thesis deals with the restoration problem in telecommunication networks. The goal is to find a cost minimal capacity capacity assignment on the edges and nodes of a network such that given demands can be satisfied even in case of the failure of an edge or node in the network. Moreover, restrictions on the routing paths (like length restrictions) and hardware constraints have to be satisfied. A Mixed Integer Programming model is presented which takes into account restoration requirements as well as hardware constraints and which abstracts from a particular restoration protocol and failure situation. This abstraction provides new insight into the structure of the network restoration problem and shows that from a mathematical point of view, the commonly used restoration techniques Link Restoration, Path Restoration and Reservation are not as different as they seem to be from a practical point of view. In addition, our model allows (but is not limited to) optimizing working capacity, intended for normal use, and spare capacity, intended for rerouting purposes in case of a failure, in one step. Furthermore, our formulation of capacity cost allows taking into account the effects of discrete, non-linear cost structures which are common in practice. Up to our knowledge, no publication in the existing literature covers all these aspects, let alone in one model, although they are of major practical interest. The model has been implemented in a Branch and Cut framework. The theoretical background of the algorithmic procedure is presented in detail, including computational complexity investigations on the pricing problem. The abstraction from a particular restoration protocol turns out to be useful both from a theoretical and computational point of view. In fact, our investigations suggest a distinction into Local Restoration and Global Restoration rather than into Link Restoration,Path Restoration, Reservation and mixtures of these concepts. In addition to the theoretical aspects of the algorithmic procedure, some implementational details are briefly discussed. Our implementation has been tested on 14 real world instances, which is described in detail. One part of the computational results consists of a comparison of optimal network cost values using diffeent restoration mechanisms, applied to securing either all single node failures, all single edge failures or both. In addition, the effects of a discrete cost structure are investigated, which has rarely been considered yet in literature. Furthermore, the cost ifference between joint and successive working and spare capacity optimization is investigated. In the second part of the computational results, several heuristics for the network restoration problem are compared with respect to both solution quality and time. This diploma thesis deals with the restoration problem in telecommunication networks. The goal is to find a cost minimal capacity capacity assignment on the edges and nodes of a network such that given demands can be satisfied even in case of the failure of an edge or node in the network. Moreover, restrictions on the routing paths (like length restrictions) and hardware constraints have to be satisfied. A Mixed Integer Programming model is presented which takes into account restoration requirements as well as hardware constraints and which abstracts from a particular restoration protocol and failure situation. This abstraction provides new insight into the structure of the network restoration problem and shows that from a mathematical point of view, the commonly used restoration techniques Link Restoration, Path Restoration and Reservation are not as different as they seem to be from a practical point of view. In addition, our model allows (but is not limited to) optimizing working capacity, intended for normal use, and spare capacity, intended for rerouting purposes in case of a failure, in one step. Furthermore, our formulation of capacity cost allows taking into account the effects of discrete, non-linear cost structures which are common in practice. Up to our knowledge, no publication in the existing literature covers all these aspects, let alone in one model, although they are of major practical interest. The model has been implemented in a Branch and Cut framework. The theoretical background of the algorithmic procedure is presented in detail, including computational complexity investigations on the pricing problem. The abstraction from a particular restoration protocol turns out to be useful both from a theoretical and computational point of view. In fact, our investigations suggest a distinction into Local Restoration and Global Restoration rather than into Link Restoration, Path Restoration, Reservation and mixtures of these concepts. In addition to the theoretical aspects of the algorithmic procedure, some implementational details are briefly discussed. Our implementation has been tested on 14 real world instances, which is described in detail. One part of the computational results consists of a comparison of optimal network cost values using different restoration mechanisms, applied to securing either all single node failures, all single edge failures or both. In addition, the effects of a discrete cost structure are investigated, which has rarely been considered yet in literature. Furthermore, the cost difference between joint and successive working and spare capacity optimization is investigated. In the second part of the computational results, several heuristics for the network restoration problem are compared with respect to both solution quality and time.
    Keywords: ddc:080
    Language: English
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 51
    Publication Date: 2020-08-05
    Keywords: ddc:080
    Language: English
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 52
    Unknown
    Manchester, U.K ; New York : Manchester University Press
    Keywords: Charity, History ; Electronic books ; Income, History, England ; Poor, History, England ; Public welfare, History, England ; Social networks, History, England
    Notes: Introduction /Alannah Tomkins,Steven King --'Not by bread only'? Common right, parish relief and endowed charity in a forest economy, c. 1600-1800 /Steve Hindle --Economy of makeshifts and the poor law: a game of chance? /Margaret Hanly --'Agents in their own concerns'? Charity and the economy of makeshifts in eighteenth-century Britain /Sarah Lloyd --Crime, criminal networks and the survival strategies of the poor in early eighteenth-century London /Heather Shore --Pawnbroking and the survival strategies of the urban poor in 1770s York /Alannah Tomkins --Kinship, poor relief and the welfare process in early modern England /Sam Barrett --Making the most of opportunity: the economy of makeshifts in the early modern north /Steven King --Conclusion /Steven King,Alannah Tomkins.
    Pages: x, 285 p.
    ISBN: 1-423-70638-2
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  • 53
    Unknown
    Oxford ; New York : Oxford University Press
    Series in affective science  
    Keywords: Affect (Psychology) ; Electronic books ; Emotions
    Pages: xvii, 1199 p.
    ISBN: 0-19-530205-2
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  • 54
    Unknown
    Mahwah, NJ : Lawrence Erlbaum
    Series in applied psychology  
    Keywords: Comportement organisationnel ; Electronic books ; Organizational behavior
    Notes: Chap. 1. The affective revolution in organizational behavior : the emergence of a paradigm / Sigal G. Barsade, Arthur P. Brief, and Sandra E. Spataro -- Chap. 2. Stress, health, and well-being at work / James Campbell Quick, Cary L. Cooper, Debra L. Nelson, Jonathan D. Quick, and Joanne H. Gavin -- Chap. 3. Self-fulfilling prophecies in organizations / Dov Eden -- Chap. 4. Understanding diversity in organizations : getting a grip on a slippery construct / Bell Rose Ragins and Jorge A. Gonzalez -- Chap. 5. Organizational justice : a fair assessment of the state of the literature -- Chap. 6. Personal reputation in organizations / Gerald R. Ferris, Fred R. Blass, Ceasar Douglas, Robert W. Kolodinsky, and Darren L. Treadway -- Chap. 7. The past, present, and future of workplace deviance research / Rebecca J. Bennett and Sandra L. Robinson -- Chap. 8. Conflicting stories : the state of the science of conflict / Kurt T. Dirks and Judi McLean Parks -- Chap. 9. Construct validation in organization behavior research / Jeffrey R. Edwards -- Chap. 10. The search for universals in cross-cultural organizational behavior / Herman Aguinis and Christine A. Henle -- Chap. 11. Good definitions : the epistemological foundation of scientific progress / Edwin A. Locke
    Pages: xxv, 470 p.
    Edition: 2nd ed
    ISBN: 1-410-60737-2
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  • 55
    Keywords: Business logistics, Management ; Electronic books ; Physical distribution of goods
    Pages: xxv, 436 p.
    Edition: 4th ed
    ISBN: 1-417-59396-2
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  • 56
    Keywords: Cognition ; Cognitive psychology ; Electronic books ; Self-organizing systems
    Notes: Intelligent behavior : a synergetic view / Hermann Haken -- Grounded in the world : developmental origins of the embodied mind / Esther Thelen -- Cognitive coordination dynamics / Scott Kelso -- What is coordinated in bimanual coordination? / Franz Mechsner and Wolfgang Prinz -- Cognition in action : the interplay of attention and bimanual coordination dynamics / Jean Jacques Temprado -- A synergetic approach to describe the stability and variability of motor behavior / Kerstin Witte ... [et al.] -- The role of synchronization in perception-action / Tin-cheun Chan ... [et al.] -- A mean-field approach to self-organization in spatially extended perception-action and psychological systems / Till Frank and Peter Beek -- Self-organizing systems show apparent intentionality / Wolfgang Tschacher, Jean-Pierre Dauwalder, and Hermann Haken -- The embodiment of intentionality / Scott Jordan -- Cognitive science, representations and dynamical systems theory / Pim Haselager, Raoul Bongers, and Iris van Rooij -- Self-steered self-organisation / Fred Keijzer -- Brain dynamics : methodological issues and applications in psychiatric and neurologic diseases / Laurent Pezard -- SIRN (synergetic inter-representation networks), artifacts and Snow's two cultures / Juval Portugali -- Dynamical systems theory : application to pedagogy / Jane Abraham
    Pages: xi, 330 p.
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  • 57
    Unknown
    Manchester ; New York : Manchester University Press
    Politics, culture, and society in early modern Britain  
    Keywords: Great Britain, Languages ; Great Britain, Languages, History ; Great Britain, Social life and customs ; Electronic books ; Literature and folklore, Great Britain ; Literature and history, Great Britain ; Oral tradition, Great Britain
    Notes: Language, literacy and aspects of identity in early modern Wales / Richard Suggett and Eryn White -- The pulpit and the pen: clergy, orality and print in the Scottish Gaelic world / Donald Meek -- Speaking of history: conversations about the past in restoration and eighteenth-century England / Daniel Woolf -- Vagabonds and minstrels in sixteenth-century Wales / Richard Suggett -- Reformed folklore? Cautionary tales and oral tradition in early modern England / Alexandra Walsham -- The genealogical histories of Gaelic Scotland / Martin MacGregor -- Constructing oral tradition: the origins of the concept in enlightenment intellectual culture / Nicholas Hudson -- 'Things said or sung a thousand times': customary society and oral culture in rural England, 1700-1900 / Bob Bushaway
    Pages: x, 286 p.
    ISBN: 1-423-70631-5
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  • 58
    Unknown
    New York : Seven Bridges Press
    Topics in contemporary philosophy  
    Keywords: Electronic books ; Semantics (Philosophy), Congresses
    Notes: Seemingly semantic intuitions / Kent Bach -- The semantic basis of externalism / Michael McKinsey -- Acquaintanceless de re belief / Robin Jeshion -- Meanings / Stephen Schiffer -- Mythical objects / Nathan Salmon -- Truth and identity / Marian David -- What is the role of a truth theory in a meaning theory? / Kirk Ludwig -- A new argument against modesty / Jonathan Sutton -- Truth and meaning / Robert Cummins -- Insensitive quantifiers / Herman Cappelen and Ernie Lepore -- Deferred demonstratives / Emma Borg -- What unarticulated constituents could not be / Lenny Clapp -- Generalized conversational implicatures and default pragmatic inferences / Anne Bezuidenhout -- Distinguishing semantics and pragmatics / Kent Bach and Anne Bezuidenhout
    Pages: x, 318 p.
    ISBN: 0-585-44941-4
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  • 59
    Unknown
    London : Kogan Page
    Keywords: Business logistics, Dictionaries ; Electronic books ; Freight and freightage, Dictionaries ; Transportation, Dictionaries
    Notes: "The terms, abbreviations, and acronyms included herein cover: Heavy vehicle technology -- Road haulage and own-account transport operations -- Passenger vehicle and public service operations -- Legal aspects of transport -- Logistics -- Supply-chain management -- Freighting by rail, sea and inland waterway -- Passenger transport by rail, sea and air -- Transport policy and planning -- Related business, accounting and information technology"--P. v
    Pages: xiv, 281 p.
    ISBN: 1-417-59388-1
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  • 60
    Publication Date: 2020-08-05
    Description: Mobile cellular communcication is a key technology in today's information age. Despite the continuing improvements in equipment design, interference is and will remain a limiting factor for the use of radio communication. This Ph. D. thesis investigates how to prevent interference to the largest possible extent when assigning the available frequencies to the base stations of a GSM cellular network. The topic is addressed from two directions: first, new algorithms are presented to compute "good" frequency assignments fast; second, a novel approach, based on semidef inite programming, is employed to provide lower bounds for the amount of unavoidable interference. The new methods proposed for automatic frequency planning are compared in terms of running times and effectiveness in computational experiments, where the planning instances are taken from practice. For most of the heuristics the running time behavior is adequate for inter active planning; at the same time, they provide reasonable assignments from a practical point of view (compared to the currently best known, but substantially slower planning methods). In fact, several of these methods are successfully applied by the German GSM network operator E-Plus. The currently best lower bounds on the amount of unavoidable (co-channel) interference are obtained from solving semidefinite programs These programs arise as nonpolyhedral relaxation of a minimum /c-parti tion problem on complete graphs. The success of this approach is made plausible by revealing structural relations between the feasible set of the semidefinite program and a polytope associated with an integer linear programming formulation of the minimum ^-partition problem. Comparable relations are not known to hold for any polynomial time solvable polyhedral relaxation of the minimum ^-partition problem. The appli cation described is one of the first of semidefinite programming for large industrial problems in combinatorial optimization.
    Keywords: ddc:080
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
    Format: application/pdf
    Format: application/postscript
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  • 61
    Unknown
    Oxford ; New York : Oxford University Press
    Studies in the history of sexuality  
    Keywords: Venice (Italy), Social conditions, To 1797 ; Electronic books ; Marriage, History, Italy, Venice ; Renaissance, Italy, Venice
    Pages: xi, 221 p.
    ISBN: 0-19-518018-6
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  • 62
    Publication Date: 2020-08-05
    Description: In der vorliegenden Dissertation untersuchen wir die Optimierung von ausfallsicheren Telekommunikationsnetzwerken. Wir präsentieren unterschiedliche gemischt-ganzzahlige Modelle für die diskrete Kapazitätsttruktu,, sowie für die Sicherung des Netzes gegen den Ausfall einzelner Komponenten. Die Modelle wurden in einer Kooperation mit der E-Plus Mobilfunk GmbH verwendet. Die theoretischen Resultate wurden in Algorithmen umgesetzt und in das von uns entiickllte Netzwerksoptimierungswerkzeug Discnet (Dimensioning Survivable Capaiitated NETworks) integriert, welches seit mehreren Jahren in der Planung bei E-Plus eingesetzt wird. Wir betrachten das Transportnetzllanungsproblem eines Telekommunikationsanbieters. Dieses Problem setzt auf logischen Kommunikattonsanforerrungen zwischen den Standorten (Knoten) des zu planenden Netzes und potentiell inslallirrbaren Verbindungen (Kanten) zwischen derselben Knotenmenge auf. Ein Kapazitätsmodell stellt die Information bereit, welche Kapazitäten auf den potentiellen Kanten verfügbar sind. Wir betrachten zwei Modelle. Entweder ist eine explizite Liste der verfügbaren Kapazittten gegeben oder eine Menge von sogenannten Basiskapazitäten, die auf jeder Kante indiviuelll kombiniert werden können. Die Basiskapazitäten müßen paarweise ganzzahlige Vielfache voneinander sein. Man beachte, daß diese Eigenschaft von den internationalen Standards PDH und SDH erfüllt wiid. Ein Ausfallsicherheitsmodell stellt die Information bereit, wie das zu planende Netz gegen den Ausfall einzelner Netzkomponenten geschützt werden soll. Wir betrachten sinnvolle Kombinationen der Modelle Diversification, Reservation und Path Restoration. Das erste Modell garantiert Ausfallsicherheit durch kommunikationsbedarfsabhängige Beschränkung des Prozentsatzes, der durch einzelne Netzkomponenten geroutet werden darf. Bei den beiden anderen Modelle können Kommunikationsbedarfe bei Ausfall einer Netzkomponente auf unterschiedliche Weise neu geroutet werden. Ziel der Planung ist eine ktstenminimlle Kapatitätsentscheidung, die eine Routenllanung aller Kommunikationsbedarfe gemäß den Ausfallsicherheitsanforderungen ermöglicht. Wir entwickeln ein Schnittebenenverfahren zur Lösung der betrachteten Optimiergngsrrobleme. Zu diesem Zweck untersuchen wir Polyeder, die mit den verschiedenen Problemen assoziiert sind. Wir präsentieren neue Klassen von Ungleichungen, entwickeln Separationsalgorithmen und Heuristiken. Mit dem Schnittebenenverfahren werden untere und obere Schranken für den Wert von Oitimallösungen berechnet, und daher ist es möglich, Qualitätsgarantien für die berechneten Löungen anzugeben. Parallel zur Beschreibung der implementierten Algorithmen präsentieren wir umfangreiche Tests mit praktisch relevanten Daten, die zu Problemen mit mehr als 2 Billionen Variablen führen.
    Keywords: ddc:080
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
    Format: application/pdf
    Format: application/postscript
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  • 63
    Publication Date: 2020-08-05
    Keywords: ddc:080
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
    Format: application/pdf
    Format: application/postscript
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  • 64
    Publication Date: 2020-08-05
    Keywords: ddc:080
    Language: German
    Type: doctoralthesis , doc-type:doctoralThesis
    Format: application/pdf
    Format: application/postscript
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  • 65
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 236-250 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To get informations on both the structure and dynamics of hydrogen chelates 1 of heteroaromatic systems, a great variety of quinazoline-2-acetonitrile chelates were synthesized (see 2-4). Similarly to the situation of the corresponding H-chelates in the pyrimidine-2-acetonitrile series, the investigation of these new derivatives 2-4 by NMR spectroscopic methods (DNMR, COSY, NOESY, ROESY, EXSY, HMQC, HMBC) confirms the presence of an equilibrium of the two possible H-chelate structures (two ‘rotamers’ I and II, i.e., (E)/(Z) isomers; see Scheme). The corresponding equilibria I ⇌ II were determined by complete 1H-NMR signal assignment at low temperatures (after freezing the rotational processes). In addition, the tautomer equilibria A ⇌ B (relative energies of the two minima of the nonsymmetrical double-well potential) for both ‘rotamers’ are ascertained by H,H and C,H couplings. The results are an important basis for the interpretation of both the UV/VIS absorptions and the dependence of fluorescence and fluorescence quantum yields on temperature.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 66
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stereoselective reactions of phthalimido-substituted radicals derived from (±)-threonine with different radical traps are reported (Scheme 3, Table 1). A strong influence of the nature of the radical trap on the stereoselectivity was noticed. Small nucleophilic radical traps gave preferentially the syn products. The observed selectivities are explained with the A1,3 strain model and depend on steric and electronic effects (Fig. 2). Reactions with electrophilic radical traps such as diphenyl diselenide gave the anti diastereoisomers with moderate stereocontrol, presumably due to stereoelectronic effects. The same stereochemical outcome, i.e., preferential formation of the anti products, was observed for the reactions of the related N-phthaloyliminium ion (Scheme 5, Table 2). The stereochemistry of the ionic reaction is rationalized by a Felkin-Anh model (Fig. 3).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 67
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclopalladation of 1,1′-azonaphthalene (= di(naphthalen-1-yl)diazene; 2) with bis(hexafluoroacetyl-acetonato)palladium(II) (3; [Pd(hfa)2]) yields the ortho-palladated complex (1,1,1,5,5,5-hexafluoropentane-2,4-dionato-κ2O,O′)[1-(naphthalen-1-ylazo-κN2)naphthalen-2-yl-κC2]palladium(II) (4) as well as the peri-palladated complex (1,1,1,5,5,5-hexafluoropentane-2,4-dionato-κ2O,O′)[8-(naphthalen-1-ylazo-κN2)naphthalen-1-yl-κC1]-palladium(II) (5); their structures were corroborated by X-ray analyses. The formation of the novel peri-metallated product 5 containing a six-membered palladacycle strongly depends upon the reaction conditions.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 68
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 342-352 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photoisomerization behavior of three mono[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines, 1, 2, and 3, and three bis[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines, 4, 5, and 6, are investigated. The synthetic product (E)-1 could be almost quantitatively (〉 96%) converted into its isomer (Z)-1 under UV light irradiation. In the cases of (E)-2 and (E)-3, a mixture of (E)/(Z) ca. 1:2 was obtained, when the same conditions were applied. The comparison of their UV spectra provides the possible explanation for these different behaviors. Furthermore, it was noticed that the (Z) → (E) isomerization of the C=C bond took place during the purification by reverse-phase high-performance liquid chromatography (RP-HPLC), and the (E)/(Z)-mixture is thus inseparable. The same feature could be observed during the isolation of the (Z,Z)-N,N′-bis[3-(4-hydroxyphenyl)prop-2-enoyl]-spermidines, (Z,Z)-4, (Z,Z)-5, and (Z,Z)-6. Nevertheless, the fractions of (Z,Z)-5 and (Z,Z)-6 were in almost pure state collected, and their 1-NMR spectra are presented.
    Additional Material: 5 Ill.
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  • 69
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 153-162 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis, absolute configuration, and olfactive evaluation of (-)-(E)-α-trans-bergamotenone (= (-)-(1′S,6′R,E)-5-(2′,6′-dimethylbicyclo[3.1.1]hept-2′-en-6′-yl)pent-3-en-2-one; (-)-1), as well as its homologue (-)-19 are reperted. The previously arbitrarily attributed absolute configuration of 1 and of (-)-α-trans-bergamotene (= (-)-(1 S,6R)-2,6-dimethyl-6-(4-methylpent-3-enyl)bicyclo[3.1. 1]hept-2-ene; (-)-2), together with those of the structurally related aldehydes (-)-3a,b and alcohols (-)-4a,b, have been rigorously assigned.
    Type of Medium: Electronic Resource
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  • 70
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 182-186 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (-)-(R)-4,4,4,4′,4′,4′-Hexafluorovaline hydrochloride ((R)-5) of 98% ee is prepared from β,β-bis(trifluoromethyl)acrylic acid (= benzyl 4,4,4-trifluoro-3-(trifluoromethyl)but-2-enoate; 1) in 4 steps with an overall yield of 9.6%. Key step is the separation of the TsOH salts of the diastereoisomers obtained by anti-Michael addition of (+)-(R)-1-phenylethylamine (2) to 1 (→ (R,R)-3). In contrast to the published (S)-chirality, the X-ray structure analysis of (R,S)-6 reveals, that (R)-chirality has to be assigned to the levorotatory (-)-4,4,4,4′,4′,4′-hexafluorovaline hydrochloride.
    Additional Material: 2 Ill.
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  • 71
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 207-218 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of tripodal dodecadentate ligands with salicylamide and bipyridine binding sites for iron(II) and iron(III) are presented.
    Additional Material: 1 Ill.
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  • 72
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of CuO'Bu with CO2, and iPr2NH in the presence of PPh3, gives the dialkylcarbamato complex [Cu(O2CNiPr2)(PPh3)2] (1). The CO2/R2NH system (R = Me, Et) in an appropriate organic medium reacts with Ag2O giving the corresponding N,N-dialkylcarbamato complexes of analytical formula [Ag(C2CNR2)] (R = Me, 2; R = Et, 3). The methyl derivative 2 was characterized by X-ray diffraction methods. Crystal data of 2: for [Ag2(O2CNMe2)2], C6H12Ag2N2O4, mol. wt. 391.9; monoclinic, space group P21/c, a = 12.08(1), b = 3.797(2), c = 11.316(7) Å, β = 113.37(6)°, V = 476.3 Å3, Z = 2, Dc = 2.732 g cm-3; μ(MoKα) = 40.64 cm-1, F(000) = 376.0; R = 0.059, Rw = 0.067; g.o.f. 1.27. The structure consists of dinuclear [(Ag2OCNMe2)2] units with slightly distorted linearly two-coordinated Ag-atoms containing bridging carbamato groups to form a substantially planar eight-membered ring with an intra-annular Ag—Ag distance of 2.837(2) Å; the dinuclear units are further joined by Ag—O bonds to form an infinite array. Compound 3, which is presumably dinuclear, as suggested by cryoscopic measurements in benzene, undergoes a structural fission with PPh3, giving the mononuclear triphenylphosphine derivative [Ag(O2CNEt2)(PPh3)2] (4). The amine-catalyzed conversion of Ag2O into Ag2CO3, in the presence of the iPr2NH/CO2 system, is also reported. Cl-Exchange from [AuCl(PPh3)] with [Ag(O2CNEt2)] (3) gives the first N,N-dialkylcarbamato complex of gold, namely [Au(O2CNEt2)(PPh3)] (5), which crystallizes in the monoclinic system: C23H25AuNO2P · 0.5 C7H16, mol. wt. 625.5, space group P21/c; a = 13.212(5), b = 12.25(1), c = 16.795(6) Å, β = 109.09(2)°, V = 2568(2) Å3, Z = 4, Dc, = 1.618 g cm-3; μ(AgKα) = 31.40 cm-1, F(000) = 1236.0; R = 0.058; Rw = 0.064; g.o.f. 2.121. The compound contains two-coordinated Au-atom, namely to the P-atom and to the O-atom of the monodentate carbamato group, the P—Au—O bond angle being 174.7(3)°. The reaction with MeI showed these compounds to react predominantly at the carbamato O-atom giving the corresponding urethanes R2NCO2Me. Evidence was gathered for the transient coordination of CO to Ag in 3.
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  • 73
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of α-diazo ketones 1a,b with 9H-fluorene-9-thione (2f) in THF at room temperature yielded the symmetrical 1,3-dithiolanes 7a,b, whereas 1b and 2,2,4,4-tetramethylcyclobutane-1,3-dithione (2d) in THF at 60° led to a mixture of two stereoisomeric 1,3-oxathiole derivatives cis- and trans-9a (Scheme 2). With 2-diazo-1,2-diphenylethanone (1c), thio ketones 2a-d as well as 1,3-thiazole-5(4H)-thione 2g reacted to give 1,3-oxathiole derivatives exclusively (Schemes 3 and 4). As the reactions with 1c were more sluggish than those with 1a,b, they were catalyzed either by the addition of LiClO4 or by Rh2(OAc)4. In the case of 2d in THF/LiClO4 at room temperature, a mixture of the monoadduct 4d and the stereoisomeric bis-adducts cis- and trans-9b was formed. Monoadduct 4d could be transformed to cis- and trans-9b by treatment with 1c in the presence of Rh2(OAc)4 (Scheme 4). Xanthione (2e) and 1c in THF at room temperature reacted only when catalyzed with Rh2(OAc)4, and, in contrast to the previous reactions, the benzoyl-substituted thiirane derivative 5a was the sole product (Scheme 4). Both types of reaction were observed with α-diazo amides 1d,e (Schemes 5-7). It is worth mentioning that formation of 1,3-oxathiole or thiirane is not only dependent on the type of the carbonyl compound 2 but also on the α-diazo amide. In the case of 1d and thioxocyclobutanone 2c in THF at room temperature, the primary cycloadduct 12 was the main product. Heating the mixture to 60°, 1,3-oxathiole 10d as well as the spirocyclic thiirane-carboxamide 11b were formed. Thiirane-carboxamides 11d-g were desulfurized with (Me2N)3P in THF at 60°, yielding the corresponding acrylamide derivatives (Scheme 7). All reactions are rationalized by a mechanism via initial formation of acyl-substituted thiocarbonyl ylides which undergo either a 1,5-dipolar electrocyclization to give 1,3-oxathiole derivatives or a 1,3-dipolar electrocyclization to yield thiiranes. Only in the case of the most reactive 9H-fluorene-9-thione (2f) is the thiocarbonyl ylide trapped by a second molecule of 2f to give 1,3-dithiolane derivatives by a 1,3-dipolar cycloaddition.
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  • 74
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 75
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    Helvetica Chimica Acta 81 (1998), S. 491-506 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a series of chiral enantiomerically pure C2-symmetric binucleating ligands is reported. Ligands of type 1-4, which consist of a phenolic or heterocyclic unit bridging two chiral dihydrooxazole rings. are readily accessible from chiral amino alcohols. Ligands 5a and 5b are composed of a cyclic urea or thiourea unit, respectively, and two 3,4-dihydro-2H-pyrrole rings containing a stereogenic center next to the N-atom. Compounds of this type are readily assembled from ethane-1,2-diamine and an imidothioic ester derived from pyroglutamic acid. These new ligands, which can coordinate two metals in close proximity to each other, are of interest regarding possible applications in asymmetric catalysis.
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  • 76
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    Helvetica Chimica Acta 81 (1998), S. 548-557 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stability constants have been measured for a series of ligands based on a 2,2′-(pyridine-2,6-diyl)bis[1H-benzimidazole] unit which forms dinuclear double-stranded helical complexes with copper(I). Variation of different structural parameters confirms the importance of the coordinate bond, the stacking interactions, and the weakly bridging pyridine units observed by X-ray crystallography. The stabilities of the complexes depend strongly on the solvent, and in MeCN, which is a good solvent for copper(I), the complexes are less stable and assemble in a stepwise manner. The interconversion of the enantiomers may be followed by 1H-NMR and takes place on a millisecond time scale around room temperature. The trends in lability are similar to those found for the stability of the complexes.
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  • 77
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    Helvetica Chimica Acta 81 (1998), S. 570-583 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oligodeoxyribonucleotides containing 7-deaza-2′-deoxy-8-methylguanosine (m8c7Gd; 2b) were prepared. For this purpose, the phosphonate 3a and the phosphoramidite 3b were synthesized and employed in solidphase oligodeoxyribonucleotide synthesis. The structures and the thermodynamic data of duplex formation of oligodeoxyribonucleotides containing 2b were investigated by temperature-dependent CD and UV spectra and compared with those containing 7-deaza-2′-deoxy-7-methylguanosine (m7c7Gd) or 7-deaza-2′-deoxy-guanosine (c7Gd; 2a). In general, compound 2b reduces the duplex stability. In case of the sequence d(m8c7G-C)4 (18), the B → Z transition was facilitated by the incorporation of 2b. Moreover, a single 7-deaza-8-methylguanine residue present in an oligodeoxyribonucleotide tract of guanine residues destabilizes the dG quadruplex significantly. This destabilization is more pronounced than in the case of 7-deazaguanine or 7-deaza-7-methyl-guanine.
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  • 78
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    Helvetica Chimica Acta 81 (1998), S. 770-780 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants and their Arrhenius parameters are obtained for the addition of a cyclic malonyl radical derived from Meldrum's acid to 20 mono- or 1,1-disubstituted alkenes in (±)-propylene oxide and for the addition of the open-chain di(tert-butyl)malonyl radical to six mono- or 1,1-disubstituted alkenes in 1,1,2-trichloro-1,2,2-trifluoroethane by time-resolved electron spin resonance spectroscopy. At room temperature, the radicals add at the unsubstituted C-atoms with rate constants ranging from 1.1. 105 M-1S-1 (acrolein) to 2.4. 106 M-1S-1 (1,1-diphenylethene). The frequency factors are in the narrow ranges of log (A/M-1S-1) = 8.7 ± 0.1 for the cyclic and log (A/M-1S-1) = 8.2 ± 0.2 for the open-chain malonyl species, whereas the activation energies vary from 12.9 kJ/mol (1,1-diphenylethene) to 21.7 kJ/mol (acrylonitrile). They correlate with the alkene ionization potentials and, more weakly, with the reaction enthalpy. No correlation was found between the activation energies and the alkene electron affinities. Hence, the results confirm and quantify the electrophilic nature of malonyl radicals in addition reactions.
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  • 79
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    Helvetica Chimica Acta 81 (1998), S. 1303-1318 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An asymmetric synthesis of (-)-(4R)-dihydroisomyricoidine (28), a 13-membered amino lactam of type A, was performed by a diastereoselective Michael addition between the spermidine derivative 3 and the commercially available optically active ethyl carboxylate 4, and the cyclization of the resulting ω-amino acid 7 using diethyl phosphorocyanidate ((EtO)2POCN), followed by a Wittig reaction to introduce the (Z)-side chain. Some side reactions are also discussed.
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  • 80
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Natural free carboxylic acids from the hadromerid sponge Diacarnus levii (Kelly-Borges and Vacelet) were esterified to yield the new cyclic norditerpene peroxides ent-muqubilin benzyl ester (= (αR,3S,6R)-α,6-dimethyl-6-[(E)-4-methyl-6-(2,6,6-trimethyl-cyclohex-1-en-1-yl)hex-3-enyl]-1,2-dioxan-3-acetic acid benzyl ester; 6, diacarnoate B methyl ester(= (αS,3R,6R)-α,6-dimethyl-6-{2-(4aS,8aS)-3,4,4a,5,6,7,8,8a-octahydro-3-oxo-2,5,5,8a-tetramethylnaphthalen-1-yl)ethyl}-1,2-dioxan-3-acetic acid methyl ester; 9), and deoxydiacarnoate B benzyl ester (= (αS,3R,6R)-α,6-dimethyl-6-{2-[(4aS,8aS)-3,4,4a,5,6,7,8,8a-octahydro-2,5,5,8a-tetramethyl-1-naphthalenyl]ethyl}-1,2-dioxan-3-acetic acid benzyl ester; 10), which were isolated following extensive chromatography. The relative configuration of the peroxide/α-methylacetate moiety of 6, 9, and 10, was directly determined from their NMR spectra. The absolute configurations of the peroxide/α-methylacetate moiety was deduced from comparative 1H-NMR data of the (S)- and (R)-phenylglycine methyl ester derivatives 7 and 8 as well as 11/13 and 12/14, all obtained from a mixture of the precursors of 3, 6, and 10. The absolute configuration at the carbobicyclic moiety of enone 9 and of 10, is identical, as established by chemical interconversion, 9 and 10 belong to the normal labdane series according to empirical CD rules, applied either directly to 9 or to the parent (+)-sclareolide-derived enone 20. In contrast, molar rotation additivity rules suggest the ent-labdane configuration for 9 and 10. The epidioxides 1-3, 6, and 10 proved active in vitro against the malaria parasite Plasmodium falciparum; especially the previously isolated methyl 3-epinuapapuanoate (2) was active against a chloroquine-resistant strain, and this with a good security index.
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  • 81
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3-Hydroxy-2-cyanoalk-2-enamides, and 2-cyano-2-(tetrahydrofuran-2-ylidene)- and 2-cyano-2-(tetrahydropyran-2-ylidene)acetamides with N-alkyl and N-aryl substituents have been synthesized in three steps from cyanoacetic acid. Their conformations were investigated by X-ray crystallography and 1H-NMR ROESY spectroscopy at room temperature. The enolic compounds 1-3 adopt an extended conformation stabilized by a strong intramolecular O—H … O=C bond both in the solid state and in (D6)DMSO solution. In contrast, the structure of the cyclic derivatives 5a,b-8a,b is solvent-dependent. In the solid state and in CDCl3 solution, the compounds adopt an extended conformation of type I or III, while, in (D6)DMSO solution, their structures undergo time-dependent (Z)/(E)-isomerization structures (of type II or IV). This observation is compatible with a dipolar transition state of rotation. The kinetics of the isomerization are controlled by the N-substituent, the N-(t-Bu) derivatives 7a and 7b having the highest barrier of rotation around the C=C bond. The whole body of experimental evidence together with the results of molecular-mechanics calculations with I-IV, indicate that, in DMSO, two (E)/(Z)-isomers with two conformations are present, and that they undergo interconversion at room temperature with four different constants. The very fast exchange rates kI,II and kIII,IV in the NMR time-scale might be responsible for the detection of only two isomers.
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  • 82
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    Helvetica Chimica Acta 81 (1998), S. 1393-1403 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new acylated dimeric secoiridoid glycoside, seemannoside A (2), has been isolated from the aerial parts of Lisianthius seemannii (GRISEB) O. KUNTZE (Gentianaceae). The structure was established by spectroscopic analysis (UV, MS, 1H- and 13C-NMR, and 2D-NMR experiments) and chemical reactions as (E-4′-O-p-coumaroyl)lisianthioside. The structure of the (Z)-isomer (seemannoside B, 3), also present in the plant, was confirmed by LC/UV/1H-NMR analysis. The active principle, 6, responsible for the antifungal activity of the apolar extract against Cladosporium cucumerinum, has been isolated. Its structure has been established by NMR spectroscopy and X-ray crystallographic analysis as a rare type of aglycone monoterpene dimer.
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  • 83
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Asymmetric Diels-Alder reaction of the pentadienoic and hexadienoic acids 2a,b with the chiral chloronitroso derivative 3 gave the primary adducts 4a,b with good-to-excellent enantioselectivity. Subsequent as- or trans-dihydroxylation and hydrogenolytic cleavage of the N—O bond led to the 5-amino-5-deoxypentono-δ-lactams 13a, 14, 15a, and 16 in the D-ribose, L-arabinose, D-xylose, and L-lyxose series, respectively, and to the 5-amino-5,6-dideoxyhexono-δ-lactams 13b and 15b in the D-allose and D-glucose series, respectively.
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  • 84
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the monomeric building block 13 and its constitutional isomer 12 of a new type of DNA analog, distamycin-NA, is presented (Schemes 1 and 2). This building block consists of a uracil base attached to a thiophene core unit via a biaryl-like axis. Next to the biaryl-like axis on the thiophene chromophore, a carboxy and an amino substituent are located allowing for oligomerization via peptide coupling. The proof of constitution and the conformational preferences about the biaryl-like axis were established by means of X-ray analyses of the corresponding nitro derivatives 10 and 11. Thus, the uracil bases are propeller-twisted relative to the thiophene core, and bidentate H-bonds occur between two uracil bases in the crystals. The two amino-acid building blocks 12 and 13 were coupled to give the dimers 15 and 16 using dicyclohexylcarbodiimide (DCC) in THF/LiCl and DMF, respectively. While the dimer 15 showed no atropisomerism on the NMR time scale at room temperature, its isomer 16 occurred as distinct diastereoisomers due to the hindered rotation around its biaryl-like axis. Variable-temperature 1H-NMR experiments allowed to determine a rotational barrier of 19 ± 1 kcal/mol in 16. The experimental data were complemented by AM1 calculations.
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  • 85
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Heating of a mixture of N,N′-(thiocarbonyl)diimidazole (= 1,1′-(carbonothioyl)bis[1H-imidazole]; 1) and 2,5-dihydro-1,3,4-thiadiazole 2a or 2b gave the 1,3-dithiolanes 4a and 4b, respectively, via a regiospecific 1,3-dipolar cycloaddition of the corresponding ‘thiocarbonyl methanides’ 3a,b onto the C=S group of 1 (Schemes 1 and 2). The adamantane derivative 4b was not stable in the presence of 1H-imidazole and during chromatographic workup. The isolated 1,3-dithiole 5 is the product of a base-catalyzed elimination of 1H-imidazole from the initial cycloadduct 4b. The formation of the S,N-acetal 6 can be rationalized by a protonation of the ‘thiocarbonyl ylide’ 3b followed by a nucleophilic addition of 1H-imidazole. With the diazo compounds 8a-e (Scheme 3) 1 underwent a regiospecific 1,3-dipolar cycloaddition to give the corresponding 2,5-dihydro-1,3,4-thiadiazole derivatives 9, which spontaneously eliminated 1H-imidazole to yield (1H-imidazol-1-yl)-1,3,4-thiadiazoles 10. The structures of 10a and 10d were established by X-ray crystallography. In the case of diazodiphenylmethane (8f), the initial cycloadduct 9f decomposed via a ‘twofold extrusion’ of N2 and S to give 1,1′-(2,2-diphenylethenylidene)bis[1H-imidazole] (11; Scheme 3).
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  • 86
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of new deoxyribose nucleosides by coupling chloropurines with modified D-ribose derivatives is reported. The methyl 2-deoxy-N-methyl-3-O-(p-toluoyl)-α-D-ribofuranosiduronamide (α-D-8) and the corresponding anomer β-D-8 were synthesized starting from the commercially available 2-deoxy-D-ribose (1) (Scheme 1). Reaction of α-D-8 with the silylated derivative of 2,6-dichloro-9H-purine (9) afforded regioselectively the N9-(2′-deoxyribonucleoside) 10 as anomeric mixture (Scheme 2), whereas β-D-8 did not react. Glycosylation of 9 or of 6-chloro-9H-purine (17) with 1,2-di-O-acetyl-3-deoxy-N-methyl-β-D-ribofuranuronamide (13) yielded only the protected β-D-anomers 14 and 18, respectively (Scheme 3). Subsequent deacetylation and dechlorination afforded the desired nucleosides β-D-11, β-D-12,15, and 16. The 3′-deoxy-2-chloroadenosine derivative 15 showed the highest affinity and selectivity for adenotin binding site vs. A1 and A2A adenosine receptor subtypes.
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  • 87
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    Helvetica Chimica Acta 81 (1998), S. 174-181 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (S)-5,5,5,5′,5′,5′-Hexafluoroleucine ((S)-13) of 81 % ee is prepared from hexafluoroacetone (l) and ethyl bromopyruvate (= ethyl 2-oxopropanoate) in 7 steps with an overall yield of 18% (Schemes 1 and 2). Key step in this sequence is the highly enantioselective reduction of the carbonyl group in α-keto ester 4 either by bakers' yeast (91 % ee) or by ‘catecholborane’ 6 utilizing an oxazaborolidine catalyst, yielding hydroxy ester (R)-5 with 99% ee. The absolute configuration was determined by X-ray analysis of the HCl adduct (S,R)-9b of (2S)-N-[(R)- l-phenylethyl]-5,5,5,5′,5′,5′-hexafluoroleucine ethyl ester.
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  • 88
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    Helvetica Chimica Acta 81 (1998) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 89
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Fmoc-Protected (Fmoc = (9H-fluoren-9-ylmethoxy)carbonyl) β-amino acids are required for an efficient synthesis of β-oligopeptides on solid support. Enantiomerically pure Fmoc-β3-amino acids β3: side chain and NH2 at C(3)(= C(β)) were prepared from Fmoc-protected (S)- and (R)-α-amino acids with aliphatic, aromatic, and functionalized side chains, using the standard or an optimized Arndt-Eistert reaction sequence. Fmoc-β2- Amino acids (β2 side chain at C(2), NH2 at C(3)(= C(β))) configuration bearing the side chain of Ala, Val, Leu, and Phe were synthesized via the Evans' chiral auxiliary methodology. The target β3-heptapeptides 5-8, a β3- pentadecapeptide 9 and a β2-heptapeptide 10 were synthesized on a manual solid-phase synthesis apparatus using conventional solid-phase peptide synthesis procedures (Scheme 3). In the case of β3-peptides, two methods were used to anchor the first β-amino acid: esterification of the ortho-chlorotrityl chloride resin with the first Fmoc-β-amino acid 2 (Method I, Scheme 2) or acylation of the 4-(benzyloxy)benzyl alcohol resin (Wang resin) with the ketene intermediates from the Wolff rearrangement of amino-acid-derived diazo ketone 1 (Method II, Scheme 2). The former technique provided better results, as exemplified by the synthesis of the heptapeptides 5 and 6 (Table 2). The intermediate from the Wolff rearrangement of diazo ketones 1 was also used for sequential peptide-bond formation on solid support (synthesis of the tetrapeptides 11 and 12). The CD spectra of the β2- and β3-peptides 5, 9, and 10 show the typical pattern previously assigned to an (M) 31 helical secondary structure (Fig.). The most intense CD absorption was observed with the pentadecapeptide 9 (strong broad negative Cotton effect at ca. 213 nm); compared to the analogous heptapeptide 5, this corresponds to a 2.5 fold increase in the molar ellipticity per residue!
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  • 90
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    Helvetica Chimica Acta 81 (1998), S. 303-306 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On irradiation (350 nm) in the presence of excess 2,3-dimethylbut-2-ene, the newly synthesized title compound 5 affords as main products the unexpected cyclopropylpyrrolidine 10 (50%) and the spiro-oxetane 9 (25%).
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  • 91
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Among seventeen different Lewis acids, TiCl4 was found to be the best catalyst for the [4 + 2] cycloaddition of cyclopentadiene to N,N′-fumaroylbis[(2R)-bornane-10,2-sultam] ((-)-1). Independently of the TiCl4 molar concentration, almost constant and complete (98-89% d.e.) diastereofacial π-selection was achieved in the Diels-Alder addition of (-)-1 to cyclopentadiene, cyclohexadiene, isoprene, and 2,3-dimethylbuta-1,3-diene.
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  • 92
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    Helvetica Chimica Acta 81 (1998), S. 353-373 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new facile synthesis of N,S- and N,Se-acetals starting from aldehydes and primary amines is presented (Schemes 3-5). These acetals are used as precursors for stereoselective radical deuteration and allylation reactions (Schemes 6 and 7, Tables 1 and 2). The stereochemical outcome of the reactions depends on the radical trap and the substituents at the N-atom. Deuterations give always anti products with moderate to high selectivities. The allylation reactions give either syn or anti products with low to moderate selectivities. The observed stereoselectivities can be explained with a model based on minimization of A1,3 strain and are controlled by steric and stereoelectronic effects.
    Additional Material: 1 Ill.
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  • 93
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Based on O-methylasparvenone (1), a N-free 5HT2C antagonist with moderate affinity (pKi = 6.7), derivatives bearing dimethylamino (7), (dimethylamino)methyl (17, 18, 21, and 22), and aminomethyl substituents (26) in place of the benzylic OH group of 1 as well as pyrrolidine- (33) and piperidine-fused derivatives (29, 43, and 45) were synthesized. In contrast to the lead structure 1, these new ligands were active in vivo in the rat. The tricycles 33 and 45 display high affinities for the 5HT2C receptor (pKi = 8).
    Additional Material: 5 Tab.
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  • 94
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal reactions of 1,2,3-trisubstituted aziridines 1 with 1,3-thiazole-5(4H)-thiones 6 in toluene yielded, in general, a mixture of two diastereoisomeric spirocyclic [2+3] cycloadducts. The formation of these products can be explained by a stereoselective electrocyclic ring opening of 1 to give an azomethine ylide 2 as the reactive intermediate, which is trapped immediately by 6 via a stereoselective 1,3-dipolar cycloaddition. Only in the case of trans-dimethyl 1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (trans-1a), four diastereoisomeric cycloadducts were formed (Scheme 4). This result is rationalized by an isomerization of the intermediate azomethine ylide cis-2a to trans -2a.
    Additional Material: 1 Ill.
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  • 95
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Due to their small mass, adjacent protons (or H-atoms) of molecular systems may exhibit quantum entanglement (or quantum correlations), even at ambient conditions. The considerable thermal disturbance and/or manybody interactions of condensed matter and the associated decoherence effect, however, cause this protonic entanglement to be restricted in space and time. Some aspects of entanglement and decoherence are mentioned. Extending our previous theoretical work, in the present paper the focus is on the possible existence of entangled protons belonging to the H-bonds of adjacent base pairs of B-type DNA. Based on the ‘working hypothesis’ that this effect does really exist, the most probable ‘positions’ for the appearance of protonic entanglement in DNA sequences are qualitatively determined. Furthermore, these ‘positions’ appear to correspond uniquely to dimers of adjacent base pairs of DNA. As a consequence, one can straightforwardly search for an enhanced appearance of such entangled H-bonds in DNA sequences of living organisms, using the existing DNA databases. A quantitative analysis of protein-coding DNA sequences of various organisms has been performed, the results of which provide strong evidence for the existence of the considered effect. The most striking finding may be summarized as follows: Quantum entanglement appears preferably between the third base of a codon and the first base of the following one. Quantitative estimates of this and further obtained results are presented. It is also shown that quantum-chemical considerations of stacking energies cannot account for the results. The new findings provide first evidence for the biological significance of entangled H-bonds.
    Additional Material: 2 Ill.
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  • 96
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 688-694 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title compounds D-10 and L-10 were prepared from 1 in eight steps and in a combined overall yield of 41-49%.
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  • 97
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of N,N'-dimethyl-2-nitroethene-1,1-diamine (8) with α,ß-unsaturated acyl isothiocyanates 9 affords 3,3-diamino-2-nitroacrylthioamides 10 (Scheme 2) in moderate-to-good yields. Cyclization of 10 under acidic conditions gives 1,3-thiazin-4-one derivatives of type 11. Oxidative cyclization of 10 with diethyl azodicaboxylate leads to 4-nitro-1,2-thiazol-5(2H)-imine derivatives 12.
    Additional Material: 2 Ill.
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  • 98
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 754-763 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The CH2Cl2 extract of Monotes engleri Gilg. (Dipterocarpaceae) showed antifungal activity against the yeast Candida albicans in our bioautographic TLC assays. After a first fractionation of the crude extract, the bioactivity was located in one of the fractions. To perform an efficient targeted isolation of the active compounds, LC/UV/MS and LC/UV/NMR analyses of the crude extract and the active fraction were performed. LC/UV/, LC/MS, and LC/NMR data (1D and 2D) allowed the identification of 1 as (2S)-2,3-dihydro-5,7-dihydroxy-{3-hydroxy-4-[(3-methylbut-2-enyl) oxy]phenyl}-4H-1-benzopyran-4-one, a new prenylated flavanone, named monoteson A. Subsequent isolation of 1 has permitted the determination of its absolute configuration on the basis of CD measurements. Theree other prenylated flavanoes 2-4 were isolated from the same extract. Compound 3 was identified as 2- (3, 5-dihydroxyphenyl) -2,3-dihydro-5, 7-dihydroxy-6, 8-bis (3-methylbut-2-enyl)-4 H-1-benzopyran-4-one, another new natural product, named monotesone B. The structures of 2 and 4 were established as selinone and lonchocarpol A, respectively. The antifungal activity against Candida albicans was determined for all compounds.
    Additional Material: 6 Ill.
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  • 99
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The disubstituted clusters[Ir4(CO)10(μ2-L—L)] with one edge-bridging ligand have a ground-state geometry with all COs terminal (L—L = (MeS)2CHMe, cluster 1) or with three edge-bridging COs (L—L = (Ph2P)2CHMe, cluste 2; L—L =Ph2P(CH2)3PPh2, cluster 3) in the solid state and in solution. A comparative 13C-NMR study of 1-3 shows that their respective ground-state geometries are merely relative minima of energy in the same kinetic profile of successive fluxional processes consisting of a merry-go-round of six COs about a unique trangular face and the rotation of terminal COs about one Ir-atom. The factors affecting the activation energy of the merry-go-round result from the relative bites of the bidentate ligands in the ground-state geometry, as shown by a comparison of the molecular structures of 2 and 3.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 100
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction between pyridoxal 5′-phosphate (PLP) with carbidopa, hydralazine, and isoniazid, in aqueous solution at variable pH and constant ionic strength of 0.1M was studied spectrophotometrically. The rate constants of formation and hydrolysis of the resulting Schiff base, and its stability were determined in a wide range of pH. A comparison is made of the formation rate constants with those of PLP with hydrazine. The reactivity shows the sequence isoniazid 〉 hydrazine 〉 carbidopa 〉 hydralazine in the whole range of pH studied. The Schiff bases studied are more stable than those formed by PLP and hexylamine and as stable as those described for the reactions of PLP with poly(L-lysine) or copolypeptides containing L-lysine.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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