Molecular rotor

Dyes with Segmental Mobility Molecular Rotors. 267... 

Haidekker MA, Nipper M, Mustafic A, Lichlyter D, Dakanali M, Theodorakis EA (2010) Dyes with segmental mobility molecular rotors, Ch. 10. In Demchenko AP (ed) Advanced Fluorescence Reporters in Chemistry and Biology I. Springer Ser Fluoresc 8 267-307... 

Probing Polymerization Dynamics with Molecular Rotors. 289... 

Applications of Molecular Rotors in Protein Sensing and Sensing of Other... 

Molecular rotors have in common that fluorescent excitation leads to an ICT, in the case of DMABN from the nitrogen in the dimethylamino electron donor group to the nitrile electron acceptor group (Fig. 1). The ICT leads to a highly polar... 

Two phenomena need to be examined to understand the interaction of a molecular rotor with its environment. First, changes of the ground-state and excited-state energies between LE and twisted states need to be examined, and second, the... 

One of the most popular applications of molecular rotors is the quantitative determination of solvent viscosity (for some examples, see references [18, 23-27] and Sect. 5). Viscosity refers to a bulk property, but molecular rotors change their behavior under the influence of the solvent on the molecular scale. Most commonly, the diffusivity of a fluorophore is related to bulk viscosity through the Debye-Stokes-Einstein relationship where the diffusion constant D is inversely proportional to bulk viscosity rj. Established techniques such as fluorescent recovery after photobleaching (FRAP) and fluorescence anisotropy build on the diffusivity of a fluorophore. However, the relationship between diffusivity on a molecular scale and bulk viscosity is always an approximation, because it does not consider molecular-scale effects such as size differences between fluorophore and solvent, electrostatic interactions, hydrogen bond formation, or a possible anisotropy of the environment. Nonetheless, approaches exist to resolve this conflict between bulk viscosity and apparent microviscosity at the molecular scale. Forster and Hoffmann examined some triphenylamine dyes with TICT characteristics. These dyes are characterized by radiationless relaxation from the TICT state. Forster and Hoffmann found a power-law relationship between quantum yield and solvent viscosity both analytically and experimentally [28]. For a quantitative derivation of the power-law relationship, Forster and Hoffmann define the solvent s microfriction k by applying the Debye-Stokes-Einstein diffusion model (2)... 

Loutfy and coworkers [29, 30] assumed a different mechanism of interaction between the molecular rotor molecule and the surrounding solvent. The basic assumption was a proportionality of the diffusion constant D of the rotor in a solvent and the rotational reorientation rate kOI. Deviations from the Debye-Stokes-Einstein hydrodynamic model were observed, and Loutfy and Arnold [29] found that the reorientation rate followed a behavior analogous to the Gierer-Wirtz model [31]. The Gierer-Wirtz model considers molecular free volume and leads to a power-law relationship between the reorientation rate and viscosity. The molecular free volume can be envisioned as the void space between the packed solvent molecules, and Doolittle found an empirical relationship between free volume and viscosity [32] (6),... 

In (8), the solvent-independent constants kr, kQnr, and Ax can be combined into a common dye-dependent constant C, which leads directly to (5). The radiative decay rate xr can be determined when rotational reorientation is almost completely inhibited, that is, by embedding the molecular rotor molecules in a glass-like polymer and performing time-resolved spectroscopy measurements at 77 K. In one study [33], the radiative decay rate was found to be kr = 2.78 x 108 s-1, which leads to the natural lifetime t0 = 3.6 ns. Two related studies where similar fluorophores were examined yielded values of t0 = 3.3 ns [25] and t0 = 3.6 ns [29]. It is likely that values between 3 and 4 ns for t0 are typical for molecular rotors. 

Fig. 7 General motif and representative structures of molecular rotors...

Replacing the phenyl group by a coumarin motif produces an important subclass of molecular rotors, represented by 17, which have found several applications in viscosity and polarity measurements [48]. On the other hand, compound 19 has a red-shifted emission as compared to 18 due to the effective delocalization of the 71-electrons in the presence of the thiophene chromophore [49]. 

Replacing the nitrile group by a benzothiazole produces an important subclass of fluorescent compounds represented by thioflavin T (25, Fig. 10). It is not clear if this compound undergoes deactivation via intramolecular rotation that would meet the criterion for a molecular rotor. The steady-state absorption and emission properties of thioflavin T has been attributed to micelle formation [53, 54], dimer and excimer formation [55, 56], and deactivation through intramolecular rotation [57]. 

Molecular rotors are useful as reporters of their microenvironment, because their fluorescence emission allows to probe TICT formation and solvent interaction. Measurements are possible through steady-state spectroscopy and time-resolved spectroscopy. Three primary effects were identified in Sect. 2, namely, the solvent-dependent reorientation rate, the solvent-dependent quantum yield (which directly links to the reorientation rate), and the solvatochromic shift. Most commonly, molecular rotors exhibit a change in quantum yield as a consequence of nonradia-tive relaxation. Therefore, the fluorophore s quantum yield needs to be determined as accurately as possible. In steady-state spectroscopy, emission intensity can be calibrated with quantum yield standards. Alternatively, relative changes in emission intensity can be used, because the ratio of two intensities is identical to the ratio of the corresponding quantum yields if the fluid optical properties remain constant. For molecular rotors with nonradiative relaxation, the calibrated measurement of the quantum yield allows to approximately compute the rotational relaxation rate kor from the measured quantum yield [Pg.284]

Molecular rotors with a dual emission band, such as DMABN or A/,A/-dimethyl-[4-(2-pyrimidin-4-yl-vinyl)-phenyl]-amine (DMA-2,4 38, Fig. 13) [64], allow to use the ratio between LE and TICT emission to eliminate instrument- and experiment-dependent factors analogous to (10). One example is the measurement of pH with the TICT probe p-A,A-dimethylaminobenzoic acid 39 [69]. The use of such an intensity ratio requires calibration with solvent gradients, and influences of solvent polarity may cause solvatochromic shifts and adversely influence the calibration. Probes with dual emission bands often have points in their emission spectra that are independent from the solvent properties, analogous to isosbestic points in absorption spectra. Emission at these wavelengths can be used as an internal calibration reference. 

A different approach to design a self-calibrating dye was proposed [70], in which a viscosity-sensitive molecular rotor (2-cyano-3-(4-dimethylaminophenyl) prop-2-enoic acid) was covalently linked to a reference dye, 7-methoxycoumarin-3-carboxylic acid, which exhibited no viscosity sensitivity (40, Fig. 13). A ratiometric measurement, that is, rotor emission relative to reference emission, was shown to be widely independent of dye concentration [70]. However, the design of such a ratiometric dye poses some challenges because of resonance energy transfer from... 

Fig. 13 Self-calibrating dyes DMA-2,4 and p-A,A-dimethylaminobenzoic acid. Compound 40 is an engineered ratiometric dye composed of a viscosity-sensitive molecular rotor and a nonviscosity-sensitive reference dye [70]...

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