A Light-Modulated Sequence-Specific DNA-Binding Peptide

Caamaño, Ana M.; Vázquez, M. Eugenio; Martı́nez-Costas, José; Castedo, Luís; Mascareñas, José L.

doi:10.1002/1521-3773(20000901)39:17<3104::aid-anie3104>3.0.co;2-0

Cited by 97 publications

(72 citation statements)

References 20 publications

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“…Vice versa, the thermodynamically favorable cis-trans conversion occurs upon irradiation with visible light or in the dark. 2 The isomerization of azobenzenes has been recently exploited for the preparation of several molecular machines 3 used as both biological 4 and photonic 5 devices. The strong geometrical difference between the extended trans form and the compact cis form in the gas phase and in solution may provide important details on the distribution and the dynamics of the azobenzene guest into hosts such as cyclodextrins 6 and crown ethers 7 or on the conformational changes of polypeptide chains.…”

Section: Introductionmentioning

confidence: 99%

Kinetics of the Z-E isomerization of monosubstituted azobenzenes in polar organic and aqueous micellar solvents

Maria¹,

Fontana²,

Gasbarri³

et al. 2008

Arkivoc

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The rates of Z-E isomerization of azobenzene and seven 4-substituted derivatives (CH3, CF3, OCH3, n-Butyl, Ot-Butyl, Br, F) have been investigated at 25 °C in ethanol, in methanol, in methanol/water mixtures and in aqueous solutions of ionic and non-ionic micelles by recording in the dark the spectral changes observed after exposure to UV light of the samples. The competitive contributions of the rotation vs. inversion mechanisms by which the isomerization of azobenzenes can occur have emerged from V-shaped Hammett plots. The obtained rate constants can be used as polarity indicators of the different micro-heterogeneous media with two main advantages with respect to other probes. Firstly they are not affected by hydrogen bonding between the substrate and the environment, as in the case of push-pull azobenzenes. Secondly, the derived substrate-independent Hammett  values allow to separate the effects of orientation of the probe from the polarity of the supramolecular aggregate.

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Section: Introductionmentioning

confidence: 99%

Kinetics of the Z-E isomerization of monosubstituted azobenzenes in polar organic and aqueous micellar solvents

Maria¹,

Fontana²,

Gasbarri³

et al. 2008

Arkivoc

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“…Photoresponsive systems [5] have attracted particular attention, since the use of light as an external switching stimulus allows for fast and clean processes (for recent reviews, see [6]). Some of the most promising and most widely used systems reported to date are i) the (Z)-1,2-di (3-thienyl)ethenes developed by Irie and co-workers [7] and successfully used by other research groups [8], ii) the ethene-based chiroptical photoswitches studied by Feringa and co-workers [9], iii) spiropyranes [10], iv) fulgides [11], and v) azobenzenes [12]. In 1984, Daub et al first reported the photochromic properties of dihydroazulenes (DHA; Scheme 1) [13].…”

mentioning

confidence: 99%

Photoswitchable Tetraethynylethene-Dihydroazulene Chromophores

Gobbi¹,

Seiler²,

Diederich³

et al. 2001

HCA

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The synthesis, characterization, and photophysical as well as electrochemical properties of the photochromic hybrid systems 11 ± 16 and 18, which contain photoswitchable tetraethynylethene (TEE; 3,4-diethynylhex-3-ene-1,5-diyne) and dihydroazulene (DHA) moieties, are presented. The molecular photoswitches were synthesized by a Sonogashira cross-coupling reaction between an appropriate TEE precursor (6 ± 10 and 17) and an iodinated DHA 1 or its vinylheptafulvene (VHF) isomer (4) (Schemes 5 ± 7). X-Ray crystal structures of five DHA derivatives (1, trans-11a, cis-11a, 12, and 13) are discussed (Figs. 2 ± 5). In all compounds, the cyclohexatriene moiety of the DHA chromophore adopts a clear boat conformation (Table 1). Presumably due to crystal-packing effects, the arylated TEE moieties in the hybrid systems show substantial distortions from planarity, with the dihedral angles between the planes of the central TEE core and the adjacent aryl substituents amounting to 448. The switching properties were investigated by electronic absorption spectroscopy. Upon light absorption, DHAs 1, 12 ± 16, and 18 underwent retro-electrocyclization in solution to give the corresponding VHFs (Figs. 6, 11, and 12). The reaction is thermally reversible, with half-lives t 1/2 between 3.9 and 5.8 h at 258 in CH 2 Cl 2 (Figs. 7 and 13 and Table 3). A comparatively slower (E) 3 (Z) isomerization process about the central CC bond of the TEE moiety was also observed. The N,N-dimethylanilino-(DMA) substituted TEE-DHA hybrid systems trans-11a and cis-11a did not react to the corresponding VHFs upon irradiation (Scheme 9). Instead, only the reversible (E) 3 (Z) photoisomerization of the TEE core occurred (Fig. 16 and Table 4). This process was further investigated for photofatigue by electronic-emission spectroscopy (Fig. 17). After protonation of the DMA group, the usual DHA 3 VHF photoreaction took place. Compound 11 represents a three-way chromophoric molecular switch with three addressable sub-units (TEE core, DHA/VHF moiety, and proton sensitive DMA group) that can undergo individual, reversible switching cycles (Scheme 9). A process modeling the function of an AND logic gate (Fig. 19) and three write/erase processes could be performed with this system. Cyclic and linear sweep-voltammetry studies in CH 2 Cl 2 ( Bu 4 NPF 6 ) revealed the occurrence of characteristic first-reduction steps in the TEE-DHA hybrid systems between À 1.6 and À 1.8 V vs. Fc/Fc (ferrocene/ferricinium couple) ( Table 5). Oxidations occur at ca. 1.10 V. After photoisomerization to the VHF derivatives, reduction steps at more positive and oxidation steps at more negative potentials were recorded. No DHA 3 VHF isomerization took place upon electrochemical oxidation or reduction (Fig. 20).

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“…Building on this successful idea of miniaturisation, Morii, Schepartz, Mascareñas Q3 and our group have enforced the proof-of-concept by using a variety of small dimerizing moieties. [7][8][9][10][11][12] Subsequently, we have shown that the attachment of the basic region peptides to a rigid scaffold, a derivative of deoxycholic acid in this case, also allows selective recognition of DNA. Indeed, our previous work on cMyc-Max b-HLH-ZIP and GCN4-bZIP proteins showed that this type of steroid-based constructs show potential for binding DNA.…”

Section: Q4mentioning

confidence: 99%

Sequence-selective DNA recognition and enhanced cellular up-take by peptide–steroid conjugates

et al. 2015

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Several GCN4 bZIP TF models have previously been designed and synthesized. However, the synthetic routes towards these constructs are typically tedious and difficult. We here describe the substitution of the Leucine zipper domain of the protein by a deoxycholic acid derivative appending the two GCN4 binding region peptides through\ud an optimized double azide–alkyne cycloaddition click reaction. In addition to achieving sequence specific dsDNA binding, we have investigated the potential of these compounds to enter cells. Confocal microscopy and flow cytometry show the beneficial influence of the steroid on cell uptake. This unique synthetic model of the bZIP TF thus combines sequence specific dsDNA binding properties with enhanced cell-uptake. Given the unique properties of deoxycholic acid and the convergent nature of the synthesis, we believe this work represents a key achievement in the field of TF mimicry

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A Light-Modulated Sequence-Specific DNA-Binding Peptide

Cited by 97 publications

References 20 publications

Kinetics of the Z-E isomerization of monosubstituted azobenzenes in polar organic and aqueous micellar solvents

Kinetics of the Z-E isomerization of monosubstituted azobenzenes in polar organic and aqueous micellar solvents

Photoswitchable Tetraethynylethene-Dihydroazulene Chromophores

Sequence-selective DNA recognition and enhanced cellular up-take by peptide–steroid conjugates

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