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991.
Ahmed E. -S. Abdel-Megied Erik B. Pedersen Carsten M. Nielsen 《Monatshefte für Chemie / Chemical Monthly》1991,122(1-2):59-70
Summary A modified synthesis of protected 2,3-dideoxyribose5 starting fromL-glutamic acid (1) is described. Reaction of5 with silylated 5-hydroxymethyluracil7 a and 5-alkoxymethyluracils7 b–e in the presence of trimethylsilyl triflate afforded an anomeric mixture of 2,3-dideoxyuridine derivatives8 a–e and9 a–e. Deprotection with methanolic ammonia and separation by chromatography gave the corresponding nucleosides10 a–e and11 a–e. Treatment of9 b–e with tri(1H-1,2,4-triazol-1-yl)phosphine oxide and subsequent reaction of12 b–e with ammonia in dioxane afforded the cytosine derivatives13 b–e which on treatment with methanolic ammonia gave the corresponding 2,3-dideoxycytidine derivatives14 b–e and15 b–e. In contrast with the parent compounds, these alkoxymethyl derivatives had no appreciable activity against human immunodeficiency virus (HIV-1).
Synthese von 2,3-Dideoxynucleosiden aus 5-Alkoxymethyluracilen
Zusammenfassung Ausgehend vonL-Glutaminsäure (1) wird eine modifizierte Synthese von geschützter 2,3-Dideoxyribose (5) beschrieben. Reaktion von5 mit silyliertem 5-Alkoxymethyluracilen7 b–e in Gegenwart von Trimethylsilyltriflat ergab anomere Mischungen der 2,3-Dideoxyuridinderivate8 a–e und9 a–e. Abspaltung der Schutzgruppe mit methanolischen Ammoniak und chromatographische Trennung ergab die entsprechenden Nucleoside10 a–e und11 a–e. Behandlung von9 b–e mit Tri(1H-1,2,4-triazol-1-yl)phosphinoxid und nachfolgende Reaktion von12 b–e mit Ammoniak in Dioxan ergab die Cytosinderivate13 b–e, welche nach Behandlung mit methanolischem Ammoniak die entsprechenden 2,3-Dideoxycytidinderivate14 b–e und15 b–e ergaben. Im Gegensatz zur Stammverbindung hatten diese Alkoxymethylderivate keine nennenswerte Wirksamkeit gegen den menschlichen Immunschwächevirus (HIV-1).相似文献
992.
Keith C Amaranatha Reddy R Baumeister U Tschierske C 《Journal of the American Chemical Society》2004,126(44):14312-14313
The first bent core mesogen carrying branched oligosiloxane units at both ends was synthesized and investigated with polarized light microscopy, DSC, X-ray diffraction of well aligned samples, and electrooptical methods. Two different antiferroelectric switching liquid crystalline phases were found. Both can be regarded as modulated smectic phases in which the molecules have extremely large tilt angles. In both mesophases, the field-induced switching takes place by rotation around the molecular long axes. This field-induced reorientation switches the layer chirality. The transition between the two mesophases is associated with a change of the tilt direction from synclinic to anticlinic. The synclinic high-temperature phase is an obliquelike ribbon phase whereas the anticlinic low-temperature phase represents a sinusoidal undulated layer structure (SmCAPA). It is proposed that the phase transition from the ribbon phase to the undulated layer structure is mainly driven by the change of the interlayer correlation. 相似文献
993.
[structure: see text] A complete overview on the alternative and competitive helices in vinylogous gamma-peptides is given, which was obtained on the basis of a systematic conformational analysis at various levels of ab initio MO theory (HF/6-31G*, DFT/B3LYP/6-31G*, PCM/HF/6-31G*). Contrary to the parent gamma-peptides, there is a strict control of helix formation by the configuration of the double bond between the C(alpha) and C(beta) atoms of the monomer constituents. (E)-Double bonds favor helices with larger pseudocycles beginning with 14- up to 27-membered hydrogen-bonded rings, whereas the (Z)-configuration of the double bonds supports a distinct preference of helices with smaller seven- and nine-membered pseudocycles showing interactions between nearest-neighbor peptide bonds. The rather stable helices of the (E)-vinylogous peptides with 22-, 24-, and 27-membered hydrogen-bonded pseudocycles have inner diameters large enough to let molecules or ions pass. Thus, they could be interesting model compounds for the design of membrane channels and monomolecular nanotubes. Since (E)- and (Z)-vinylogous gamma-amino acids and their oligomers are synthetically accessible, our study may stimulate structure research in this novel field of foldamers. 相似文献
994.
Chen B Baumeister U Pelzl G Das MK Zeng X Ungar G Tschierske C 《Journal of the American Chemical Society》2005,127(47):16578-16591
T-shaped polyphilic triblock molecules, consisting of a rodlike p-terphenyl unit, a hydrophilic and flexible laterally attached oligo(oxyethylene) chain terminated by an 1-acylamino-1-deoxy-D-sorbitol unit, and two end-attached lipophilic alkyl chains, have been synthesized by palladium-catalyzed cross-coupling reactions as the key steps. The thermotropic liquid crystalline behavior of these compounds was investigated by polarized light microscopy, differential scanning calorimetry (DSC), and X-ray scattering. We investigated the mode of self-organization as a function of the length and position of the lateral polar chain and the length of the terminal alkyl chains. Depending on the size of the polar and lipophilic segments, a series of unusual liquid crystalline phases was detected. In three of these phases, the space is divided into three distinct periodic subspaces. In addition to a hexagonal channeled layer phase (ChL(hex)) consisting of layers that are penetrated by polar columns, there are also two honeycomb-like network structures formed by square (Col(squ)/p4mm) or pentagonal cylinders (Col(squ)/p4gm). The cylinder walls consist of the terphenyl units fused by columns of alkyl chains, and the interior contains the polar side chains. In addition, a hexagonal columnar phase was observed in which the polar columns are organized in a continuum of terphenyls and alkyl chains with an organization of the terphenyl cores tangentially around the columns with the long axis perpendicular to the columns. For one compound, a reversal of birefringence was observed, which is explained by a reorientation of the terphenyl cores. The addition of protic solvents induces lamellar phases. 相似文献
995.
Schleifenbaum A Stier G Gasch A Sattler M Schultz C 《Journal of the American Chemical Society》2004,126(38):11786-11787
We developed a probe for investigating protein kinase C (PKC) activity in living cells. The probe is based on a fragment of pleckstrin enclosed by two FRET-capable fluorophores. PKC activity modulation was reliably followed by FRET change in vitro and in vivo. The probe responds quickly to PKC activation by phorbol ester. FRET changes were reversible when PKC inhibitors were administered. Stimulation of cellular signaling pathways using histamine or bradykinin triggered PKC in a physiologically relevant way. 相似文献
996.
Chen B Baumeister U Diele S Das MK Zeng X Ungar G Tschierske C 《Journal of the American Chemical Society》2004,126(28):8608-8609
A series of three novel liquid crystalline amphiphilic molecules is reported which are composed of three incompatible molecular parts, a rigid terphenyl core, two lipophilic decyloxy chains in the terminal 4- and 4' '-positions, and a polar group in the lateral 2'-position. The polar group comprises a polyether chain, an amide group, and a polyhydroxyalkyl end group (1-acylamino-1-deoxy-d-sorbitol derivatives). The self-organization of these compounds was studied by polarized light microscopy, differential scanning calorimetry, and different X-ray diffraction techniques. These investigations confirm a novel liquid crystalline phase with a square 2D-lattice (square columnar mesophase, plane group p4mm). This structure is built up by a set of three distinct columns, namely columns containing the polar lateral groups, columns incorporating the alkyl chains, and ribbons of the rodlike terphenyl units. The calamitic cores form walls bounding square-shaped channels occupied by the microsegregated polar lateral chains. The lipophilic columns containing alkyl chains are at the corners interconnecting the aromatic rods end-to-end. 相似文献
997.
Carsten Knapp 《Journal of fluorine chemistry》2006,127(7):916-919
The small di- and triatomic molecules [SN]+ and [SNS]+ have shown versatile chemistries and [SNS]+ is an important starting reagent for many sulfur-nitrogen radicals. However, their chemistry is limited to the more polar solvents (e.g. SO2). In this work an attempt is made to increase their solubility in less polar solvents by exchange of the usual [MF6]− (M = As, Sb) anions by the large and weakly coordinating [Al(OC(CF3)3)4]−. As expected the metathesis reactions of [SN][AsF6] and [SNS][SbF6] with Li[Al(OC(CF3)3)4] in liquid sulfur dioxide resulted in the formation of the insoluble Li[SbF6], which is the driving force for these metathesis reactions. The characterization of the compounds by IR and multinuclear NMR revealed that [SNS]+ formed a [Al(OC(CF3)3)4]− salt in a clean reaction. A preliminary crystal structure of [SNS][Al(OC(CF3)3)4] is presented. The solubility of [SNS][Al(OC(CF3)3)4] in CH2Cl2 is significantly increased with respect to the corresponding [MF6]− salts, and potentially opens up new areas of [SNS]+ chemistry. The reaction of the more reactive [SN]+ with Li[Al(OC(CF3)3)4] was less clear. Multinuclear NMR and IR spectra were consistent with the formation of [SN][Al(OC(CF3)3)4], which also showed significant decomposition. 相似文献
998.
Prehm M Cheng XH Diele S Das MK Tschierske C 《Journal of the American Chemical Society》2002,124(41):12072-12073
Novel lamellar mesophases which are quite distinct from conventional smectic mesophases were obtained with a bolaamphiphilic triblock molecule composed of a rigid biphenyl core, two polar 2,3-dihydroxypropoxy groups in the terminal 4- and 4'-positions, and a semiperfluorinated chain [O(CH2)6C10F21] in the lateral 3-position. The competitive combination of microsegregation and rigidity in this molecule leads to layer structures in which the bolaamphiphilic cores segregate from the lateral chains into distinct sublayers. In these sublayers the biphenyl cores are aligned parallel to the layer planes. Decreasing the temperature leads to a subsequent inset of orientational and positional order of the biphenyl unit, which leads to a transition from an uniaxial SmA phase to a biaxial SmAb phase and finally to a mesophase with an additional periodicity within the aromatic sublayers. Here, microsegregation occurs on two distinct levels: The segregation of the nonpolar chains from the aromatic cores leads to the "bulk" layer structure and segregation of polar and aromatic subunits within the aromatic sublayers gives rise to an additional periodicity within the aromatic sublayers. These phases can be regarded as smectic phases built up by quasi-2D layers with nematic, respectively SmA-like order, separated by isotropic layers of the lateral chains. 相似文献
999.
Simon Greiner Benjamin Schwarz Mark Ringenberg Maximilian Dürr Ivana Ivanovic-Burmazovic Maximilian Fichtner Montaha Anjass Carsten Streb 《Chemical science》2020,11(17):4450
Polyoxometalates are key materials for energy conversion and storage due to their unique chemical tunability and electrochemical reactivity. Herein, we report that functionalization of molecular vanadium oxides, polyoxovanadates, with redox-inert Ca2+ cations leads to a significant increase in their electron storage capabilities. The electrochemical performance of the Ca2+-functionalized dodecavanadate [Ca2V12O32Cl(DMF)3]2− (={Ca2V12}) was thus compared with that of the precursor compound (H2NMe2)2[V12O32Cl]3− (={V12}). {Ca2V12} can store up to five electrons per cluster, while {V12} only shows one reversible redox transition. In initial studies, we demonstrated that {Ca2V12} can be used as an active material in lithium-ion cathodes. Our results show how redox-inert cations can be used as structural and electrostatic stabilizers, leading to major changes in the redox-chemistry of polyoxovanadates.The enhanced redox-activity of a molecular vanadium oxide cluster upon functionalization with redox-inert Ca2+ ions is reported together with initial insights into its performance as a lithium ion battery cathode. 相似文献
1000.
Zucht HD Lamerz J Khamenia V Schiller C Appel A Tammen H Crameri R Selle H 《Combinatorial chemistry & high throughput screening》2005,8(8):717-723
This report will provide a brief overview of the application of data mining in proteomic peptide profiling used for medical biomarker research. Mass spectrometry based profiling of peptides and proteins is frequently used to distinguish disease from non-disease groups and to monitor and predict drug effects. It has the promising potential to enter clinical laboratories as a general purpose diagnostic tool. Data mining methodologies support biomedical science to manage the vast data sets obtained from these instrumentations. Here we will review the typical workflow of peptide profiling, together with typical data mining methodology. Mass spectrometric experiments in peptidomics raise numerous questions in the fields of signal processing, statistics, experimental design and discriminant analysis. 相似文献