Postsynthetic Derivatization of Fluorophores with α-Sulfo-β-alanine Dipeptide Linker. Application to the Preparation of Water-Soluble Cyanine and Rhodamine Dyes

Romieu, Anthony; Brossard, Dominique; Hamon, Maxime; Outaabout, Hakim; Portal, Christophe; Renard, Pierre

doi:10.1021/bc7003268

Cited by 44 publications

(41 citation statements)

References 39 publications

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“…[17] Compounds 7-H,SO 3 H,Y are readily available by sulfonation of the corresponding precursors 7-H,H,Y (Y = H, CO 2 Et), which, in turn, can be easily synthesized from phenol 5-H,TBDMS [18] (Scheme 4; TBDMS = tert-butyldimethylsilyl). The appropriate protecting groups should be compatible with the conditions of the diazoketone synthesis.…”

Section: ][9h]xanthen-3-one Fragmentmentioning

confidence: 99%

“…The appropriate protecting groups should be compatible with the conditions of the diazoketone synthesis. [17] First, the sterically hindered free carboxyl group CO 2 R (R= H) in compound 7-R,X,Y was protected as an allyl (All) ester, then the sulfonic acid residues were alkylated with Meerwein salt [triethyloxonium tetrafluoroborate (Et 3 OBF 4 )] in the presence of a base. Another challenge was to provide additional protection for at least one of the two different carboxyl groups in the presence of the sulfonic acid residue(s) in such a way that these reaction centers may be addressed independently and in a certain reaction sequence.…”

Section: ][9h]xanthen-3-one Fragmentmentioning

confidence: 99%

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Masked Rhodamine Dyes of Five Principal Colors Revealed by Photolysis of a 2‐Diazo‐1‐Indanone Caging Group: Synthesis, Photophysics, and Light Microscopy Applications

Belov

Mitronova

Bossi

et al. 2014

Chemistry A European J

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Caged rhodamine dyes (Rhodamines NN) of five basic colors were synthesized and used as "hidden" markers in subdiffractional and conventional light microscopy. These masked fluorophores with a 2-diazo-1-indanone group can be irreversibly photoactivated, either by irradiation with UV- or violet light (one-photon process), or by exposure to intense red light (λ∼750 nm; two-photon mode). All dyes possess a very small 2-diazoketone caging group incorporated into the 2-diazo-1-indanone residue with a quaternary carbon atom (C-3) and a spiro-9H-xanthene fragment. Initially they are non-colored (pale yellow), non-fluorescent, and absorb at λ=330-350 nm (molar extinction coefficient (ε)≈10(4) M(-1) cm(-1)) with a band edge that extends to about λ=440 nm. The absorption and emission bands of the uncaged derivatives are tunable over a wide range (λ=511-633 and 525-653 nm, respectively). The unmasked dyes are highly colored and fluorescent (ε=3-8×10(4) M(-1) cm(-1) and fluorescence quantum yields (ϕ)=40-85% in the unbound state and in methanol). By stepwise and orthogonal protection of carboxylic and sulfonic acid groups a highly water-soluble caged red-emitting dye with two sulfonic acid residues was prepared. Rhodamines NN were decorated with amino-reactive N-hydroxysuccinimidyl ester groups, applied in aqueous buffers, easily conjugated with proteins, and readily photoactivated (uncaged) with λ=375-420 nm light or intense red light (λ=775 nm). Protein conjugates with optimal degrees of labeling (3-6) were prepared and uncaged with λ=405 nm light in aqueous buffer solutions (ϕ=20-38%). The photochemical cleavage of the masking group generates only molecular nitrogen. Some 10-40% of the non-fluorescent (dark) byproducts are also formed. However, they have low absorbance and do not quench the fluorescence of the uncaged dyes. Photoactivation of the individual molecules of Rhodamines NN (e.g., due to reversible or irreversible transition to a "dark" non-emitting state or photobleaching) provides multicolor images with subdiffractional optical resolution. The applicability of these novel caged fluorophores in super-resolution optical microscopy is exemplified.

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Section: ][9h]xanthen-3-one Fragmentmentioning

confidence: 99%

Section: ][9h]xanthen-3-one Fragmentmentioning

confidence: 99%

Masked Rhodamine Dyes of Five Principal Colors Revealed by Photolysis of a 2‐Diazo‐1‐Indanone Caging Group: Synthesis, Photophysics, and Light Microscopy Applications

Belov

Mitronova

Bossi

et al. 2014

Chemistry A European J

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“…Benzoindole pentamethine cyanine dyes have been extensively applied in the fields of biomacromolecule fluorescent labeling, [1][2][3] nonlinear optical materials 4 and optical disc storage, [5][6] due to their stability and excellent spectral properties, including large molar extinction coefficients, broad wavelength tunability, and particularly their high near-infrared (NIR) absorption and emission wavelengths.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structure, Spectral and Thermodynamic Properties of One Benzoindole Pentamethine Cyanine Dye

Zhang

Zhao

et al. 2013

J Chinese Chemical Soc

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One benzoindole pentamethine cyanine dye was synthesized and characterized by 1 H NMR, IR, MS and UV-Vis spectra. The UV-Vis absorption and fluorescence spectra of the dye in chloroform, dimethyl sulfoxide, acetone, ethanol and methanol were investigated, and the l max of the dye was in the region 682.0-689.0 nm with large molar extinction coefficients (e > 10 5 M -1 cm -1 ) in different solvents. The structure of the dye was also characterized and analyzed by X-ray diffraction. Crystallographic data revealed that the dye belonged to orthorhombic, with space group P2 1 2 1 2 1 , a = 10.059(2) Å, b = 15.098(4) Å, c = 24.989(6) Å, V = 3794.8(15) Å 3 , Z = 4. The C-H ¼ F intermolecular hydrogen bonds were displayed in the molecular system, which were effective in the molecular packing. The aggregation behavior and thermodynamic properties of the dye in aqueous methanol solution were also studied by means of UV-Vis spectroscopy methods. The results indicated that the dye existed monomer-dimer equilibrium in aqueous methanol solutions. The fundamental properties of the dye, such as the dimeric association constant K D , the dimeric free energy DG D , the dimeric entropy DS D , and the dimeric enthalpy DH D were determined. The DH D of the dye was -46.0 kJ mol -1 .

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“…F d (" v) describes the emission intensity of the donor and e(" v) the extinction coefficient of the acceptor at the wavenumber " v. Taking the refractive index in the sol-gel film to be 1.45 [34] and the extinction coefficient for Texas Red at its maximum absorption as 85 000 m À1 cm À1 , [35] then the Fçrster distance for energy transfer in the sol-gel film from Equation (1) is 60.3 . In water, the value obtained for R o is 61.5 .…”

Section: Steady-state Spectramentioning

confidence: 99%

The Influence of Silver Nanostructures Formed in situ in Silica Sol–Gel Derived Films on the Rate of Förster Resonance Energy Transfer

et al. 2011

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The efficiency of Förster resonance energy transfer (FRET) can be enhanced in the presence of a metal. Herein, we demonstrate the increased efficiency for a novel model sensor system where FRET is shown to occur between Rhodamine 6G in the bulk sol-gel matrix and Texas Red, which is held a fixed distance away by covalent attachment onto a silane spacer. Silver colloids are formed using light to initiate the reduction of a silver salt, which can be achieved at controlled locations within the film. Both the fluorescence intensity and lifetime maps and analysis indicate that an enhanced FRET efficiency has been achieved in the presence of silver nanoparticles. An increase in efficiency of 1.2-1.5 times is demonstrated depending on the spacer used. The novelty of our approach lies in the method of silver-nanoparticle formation, which allows for the accurate positioning of the silver nanoparticles and hence selective fluorescence enhancement within a biocompatible host material. Our work gives a practical demonstration of metal-enhanced FRET and demonstrates the ability of such systems to be developed for molecular-recognition applications that could find use in lab-on-a-chip technologies.

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Postsynthetic Derivatization of Fluorophores with α-Sulfo-β-alanine Dipeptide Linker. Application to the Preparation of Water-Soluble Cyanine and Rhodamine Dyes

Cited by 44 publications

References 39 publications

Masked Rhodamine Dyes of Five Principal Colors Revealed by Photolysis of a 2‐Diazo‐1‐Indanone Caging Group: Synthesis, Photophysics, and Light Microscopy Applications

Masked Rhodamine Dyes of Five Principal Colors Revealed by Photolysis of a 2‐Diazo‐1‐Indanone Caging Group: Synthesis, Photophysics, and Light Microscopy Applications

Synthesis, Crystal Structure, Spectral and Thermodynamic Properties of One Benzoindole Pentamethine Cyanine Dye

The Influence of Silver Nanostructures Formed in situ in Silica Sol–Gel Derived Films on the Rate of Förster Resonance Energy Transfer

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