Ab Initio Electronic Circular Dichroism of Fullerenes, Single‐Walled Carbon Nanotubes, and Ligand‐Protected Metal Nanoparticles

Noguez, Cecilia; Hidalgo, Francisco

doi:10.1002/chir.22348

Cited by 21 publications

(8 citation statements)

References 75 publications

(197 reference statements)

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“…[54] CPL probes for chiral species The high sensitivity of circularly polarized luminescence (CPL) towards subtle changes in the coordination environment of chiral europium complexes makes it a very useful technique to use in addressing chiral systems. Often, significant changes in the total emission spectra do not occur, whereas the high emission dissymmetry factors, gem, found in lanthanide complexes, where g = 2(IL--IR)/ (IL + IR) varying from 0.1 to 1.38) [55] , allow CPL to be used to monitor the binding of chiral analytes. Using a racemic mixture of the Eu 3+ complex, an induced CPL response can be monitored following interaction with a chiral analyte.…”

Section: Dna/rna Recognition Via a Template Reactionmentioning

confidence: 99%

Responsive, Water‐Soluble Europium(III) Luminescent Probes

Shuvaev

Starck

Parker

2017

Chemistry A European J

117

103

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Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. E-mail: david.parker@dur.ac.uk; sergey.shuvaev@dur.ac.uk Abstract: The design principles, mechanism of action and performance of europium(III) complexes that serve as strongly emissive and responsive molecular probes in water are critically discussed. Examples of systems designed to assess pH, selected metal ions and anions, including chiral species, as well as selected small molecules and biopolymers are considered, and prospects evaluated for improved performance in more complex biological media such as in bio--fluids and within living cells. Modulation of the emission spectral form, lifetime and degree of circular polarisation can be used to quantify the spectral response and permit calibration. IntroductionThe genesis of lanthanide bio--imaging probes can be traced to two discoveries: the observation of the red emission of europium by Crookes in 1885 and the report of its sensitised emission made by Weissman in 1942 [1] . Each discovery epitomises the advantageous optical features of lanthanide complexes - narrow bands in emission with energies only slightly affected by the nature of the ligand, and a large separation (a "pseudo--Stokes' shift") between the absorbing (ligand--antenna) and emitting (lanthanide ion) photon energies. These favourable optical properties create a myriad of opportunities to devise responsive systems by judicious ligand design. Europium(III) complexes have particular advantages over other lanthanide complexes in biologically relevant applications: the higher transparency of biological tissue towards the red region of the visible spectrum; their high inherent brightness and low sensitivity to quenching by oxygen; the presence of three excited states ( 5 D2, 5 D1 and 5 D0) spanning the range 17500--21000 cm --1 that are lower in energy than the triplet levels of many different types of ligands; the presence of an environmentally insensitive magnetic--dipole transition 5 D0 to 7 F1 in the luminescence spectrum, (Figure 1), that can be used as an internal reference to the hypersensitive transition bands around 620 ( 5 D0 --7 F2) and 700 nm ( 5 D0 to 7 F4), and the high emission anisotropy factors, gem, in circularly polarised luminescence (CPL) spectra.

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Section: Dna/rna Recognition Via a Template Reactionmentioning

confidence: 99%

Responsive, Water‐Soluble Europium(III) Luminescent Probes

Shuvaev

Starck

Parker

2017

Chemistry A European J

117

103

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“…In comparison with circular dichroism (CD) spectroscopy, CPL spectroscopy provides higher sensitivity, and its ability to resolve transitions otherwise invisible by conventional luminescence spectroscopy renders it advantageous over total emission spectral analysis. Strong CPL signals of europium and terbium complexes have been exploited to create pH, temperature, protein, and anion‐sensitive CPL probes, whose dissymmetry factor has been monitored as a function of pH or added analyte. Deviations in cellular uptake of different enantiomers can also be exploited, with the advent of chiral luminescence microscopy, by detecting the CPL signal from enantiomeric complexes in cellulo …”

Section: Figurementioning

confidence: 99%

Monitoring of the ADP/ATP Ratio by Induced Circularly Polarised Europium Luminescence

2018

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A series of three europium complexes bearing picolyl amine moieties was found to possess differing binding affinities towards Zn and three nucleotides: AMP, ADP, and ATP. A large increase in the total emission intensity was observed upon binding Zn , followed by signal amplification upon the addition of nucleotides. The resulting adducts possessed strong induced circularly polarised emission, with ADP and ATP signals of opposite sign. Model DFT geometries of the adducts suggest the Δ diastereoisomer is preferred for ATP and the Λ isomer for ADP/AMP. This change in sign allows the ADP/ATP (or AMP/ATP) ratio to be assessed by monitoring changes in the emission dissymmetry factor, g .

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“…For a deeper insight, we report the ECD spectrum of 1 measured in the solid state as microcrystalline sample (Figure B). This latter technique reveals primarily the specific chiroptical response of the conformation found in the crystals (although it is also sensitive to intercrystalline interactions) . The consistency of the visible ECD band of 1 in solution and in the solid state demonstrates that the Fc helicity is preserved—at least in part—in solution.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and structure analysis of ferrocene‐containing pseudopeptides

et al. 2018

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Ferrocene with its aromaticity and facile redox properties is an attractive moiety to be incorporated into functional moieties. Medicinal applications of ferrocene are well known and ferrocene itself shows cytotoxic and antianemic properties. In this article, we will describe the synthesis and the structure analysis of two pseudopeptides containing a ferrocene moiety as N-terminal group. After purification, Fc-l-Phe-d-Oxd-OBn [l-Phel-phenylalanine; d-Oxd(4R,5S)-4-Methyl-5-carboxy-oxazolidin-2-one] appears as bright brown solid that spontaneously forms brown needles. The X-ray diffraction of the crystals shows the presence of strong π interactions between the ferrocenyl moiety and the phenyl rings, while no NH•••OC hydrogen bonds are formed. This result is confirmed by FT-IR and H NMR analysis. In contrast, both FT-IR and H NMR analysis suggest that Fc-(l-Phe-d-Oxd) -OBn forms a turn conformation stabilized by intramolecular NH•••OC hydrogen bonds in solution. Chiroptical spectroscopies (ECD and VCD) substantially confirmed the absence of a well-defined folded structure. The presence of the Fc moiety is responsible for specific ECD signals, one of which displayed pronounced temperature dependence and is directly related with the helicity assumed by the Fc core. Solid-state ECD spectra were recorded and rationalized on the basis of the X-ray geometry and quantum-mechanical calculations.

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Ab Initio Electronic Circular Dichroism of Fullerenes, Single‐Walled Carbon Nanotubes, and Ligand‐Protected Metal Nanoparticles

Cited by 21 publications

References 75 publications

Responsive, Water‐Soluble Europium(III) Luminescent Probes

Responsive, Water‐Soluble Europium(III) Luminescent Probes

Monitoring of the ADP/ATP Ratio by Induced Circularly Polarised Europium Luminescence

Synthesis and structure analysis of ferrocene‐containing pseudopeptides

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