- Synthesis of a non-cationic, water-soluble perylenetetracarboxylic diimide and its interactions with G-quadruplex-forming DNA
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A number of N,N′-disubstituted perylenetetracarboxylic diimides have been reported to bind effectively to DNA that adopts G-quadruplex motifs. In some cases, this binding may actively drive the transition from single-strand DNA to the quadruplex form. The perylenediimides in the reported cases all have amine-containing side chains, which are thought to interact with the grooves of the quadruplex and help dictate the selectivity of these compounds for quadruplex versus duplex DNA. We synthesized a polyethyleneglycol-swallowtailed (PEG-tailed) perylenediimide that is water-soluble even though it is uncharged. Binding to duplex and quadruplex DNA of this perylenediimide was studied by fluorescence quenching titrations under a variety of salt conditions, and the compound's effect on quadruplex formation was studied by non-denaturing gel electrophoresis. Our results indicate that while the molecule binds to single-stranded DNA quite effectively and with selectivity, it does not drive the transition of the DNA to the tetrameric quadruplex structure, supporting the idea that charge neutralization is a key component of perylene compounds that stabilize tetrameric quadruplexes.
- Samudrala, Ramakrishna,Zhang, Xu,Wadkins, Randy M.,Mattern, Daniell Lewis
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- Templated Chromophore Assembly on Peptide Scaffolds: A Structural Evolution
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The use of a template that bears pre-programmed receptor sites for selectively accommodating chromophores at given positions is an attractive approach for engineering artificial-light-harvesting systems. Indulging this line of thought, this work tackles the creation of tailored antenna architectures with yellow, red and blue chromophores, exploiting three dynamic covalent reactions simultaneously, namely disulfide exchange, acyl hydrazone, and boronic ester formations. The effect of various structural modifications, such as the chromophores as well as their spatial organization (distance, orientation, order) on the energy transfer within the antennas was studied by means of steady-state UV/Vis absorption and fluorescence spectroscopies. This systematic study allowed for a significant improvement of the energy-transfer efficiencies to a noticeable 22 and 15 % for the yellow and red donors, respectively, across the chromophores to the blue acceptor. Metadynamics simulations suggested that the conformational properties of the antennas are driven by intramolecular chromophoric stacking interactions that, upon forcing the α-helix to fold on itself, annul any effects deriving from the programming of the spatial arrangement of the receptor sides in the peptide backbone.
- Rocard, Lou,Wragg, Darren,Jobbins, Samuel Alexander,Luciani, Lorenzo,Wouters, Johan,Leoni, Stefano,Bonifazi, Davide
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supporting information
p. 16136 - 16148
(2018/10/15)
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- Amino acid motifs in natural products: Synthesis of O-acylated derivatives of (2S,3S)-3-hydroxyleucine
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(2S,3S)-3-Hydroxyleucine can be found in an increasing number of bioactive natural products. Within the context of our work regarding the total synthesis of muraymycin nucleoside antibiotics, we have developed a synthetic approach towards (2S,3S)-3- hydroxyleucine building blocks. Application of different protecting group patterns led to building blocks suitable for C- or N-terminal derivatization as well as for solid-phase peptide synthesis. With respect to according motifs occurring in natural products, we have converted these building blocks into 3-O-acylated structures. Utilizing an esterification and cross-metathesis protocol, (2S,3S)-3-hydroxyleucine derivatives were synthesized, thus opening up an excellent approach for the synthesis of bioactive natural products and derivatives thereof for structure activity relationship (SAR) studies.
- Ries, Oliver,Bueschleb, Martin,Granitzka, Markus,Stalke, Dietmar,Ducho, Christian
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supporting information
p. 1135 - 1142
(2014/06/09)
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- TETRAHYDRONAPHTHYRIDINE AND RELATED BICYCLIC COMPOUNDS FOR INHIBITION OF RORgamma ACTIVITY AND THE TREATMENT OF DISEASE
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The invention provides tetrahydronaphthyridine and related compounds, pharmaceutical compositions, methods of inhibiting RORγ activity, reducing the amount of IL-17 in a subject, and treating immune disorders and inflammatory disorders using such tetrahydronaphthyridine and related compounds.
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Paragraph 0316
(2013/12/03)
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- Synthesis of donor-σ-perylenebisimide-acceptor molecules having PEG swallowtails and sulfur anchors
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Donor-σ-Acceptor (D-σ-A) molecules, arrayed in a monolayer between electrodes, can serve as molecular rectifiers. Using perylene-3,4,9,10-tetracarboxylic bisimide (PBI) as the acceptor allows the attachment of the donor group to one imide nitrogen and a solubilizing swallowtail, normally a long (e.g., C19) alkane connected at midchain, on the other. Such an alkyl tail facilitates the formation of Langmuir-Blodgett (LB) monolayers. We have employed several modified swallowtails to make new D-σ-A molecules: poly(ethylene glycol) (PEG) swallowtails with 6 ether oxygens or with 4 ether oxygens to promote hydrophilicity in orienting LB monolayers, and alkyl swallowtails ending with sulfur anchors (thioacetate, thiol, or methyl disulfide) to stabilize attachment of the D-σ-A molecules to gold electrodes. The preparation and characterization of D-σ-A molecules containing combinations of these swallowtails with pyrene, ferrocene, and tetramethylphenylenediamine donor groups is described.
- Kota, Rajesh,Samudrala, Ramakrishna,Mattern, Daniell Lewis
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p. 9641 - 9651
(2013/01/15)
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- New approaches towards monoamino polyglycerol dendrons and dendritic triblock amphiphiles
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In order to improve the water solubility of nonpolar compounds such as drugs or dyes, new amphiphilic molecules are needed. In this paper we describe a new class of triblock amphiphiles that we have synthesized by a straightforward convergent approach. These amphiphiles each consist of a nonpolar biphenyl core and a polar shell based on various generations of monoamino polyglycerol dendrons, coupled to the core through amide linkages (1). For the synthesis of these monoamino dendrons we applied a simple iterative two-step process based on allylation of an alcohol group and catalytic dihydroxylation. As starting materials, D,L-serine/serinol and - in a second, similar pathway - commercially available triglycerol were used. The transport behavior of these defined triblock amphiphiles was then investigated with the nonpolar dye Nile Red in water. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Wyszogrodzka, Monika,Moews, Katrin,Kamlage, Stefan,Wodzinska, Joanna,Plietker, Bernd,Haag, Rainer
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