Tuning of dye optical properties by environmental effects: a QM/MM and experimental study

Frate, Gianluca Del; Bellina, Fabio; Mancini, Giordano; Marianetti, Giulia; Minei, Pierpaolo; Pucci, Andrea; Barone, Vincenzo

doi:10.1039/c6cp00841k

Cited by 11 publications

(15 citation statements)

References 48 publications

(66 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Note that PCM was already shown to well reproduce the electrostatic effects of PMMA environment in a previous work. [29] Maximum absorption wavelength was found at about 321 nm for both systems, in line with the calculations for the solvents reported above. The other two peaks take place at about 298 and 268 nm and appear as shoulders of the main first absorption band.…”

Section: Resultssupporting

confidence: 88%

“…DPAP was docked into the cavity of a pre-equilibrated atactic PMMA matrix following a similar protocol of a previous study. [29] The DPAP structure was embedded into the polymer matrix avoiding close contacts with the surrounding polymer chains and the system was minimized via the steepest descent algorithm until a energy threshold of 0.5 kJ/mol was reached. Within the simulated time interval, DPAP remained trapped into the PMMA cavity, displaying no translational motion and little reorientational freedom ( vide infra ).…”

Section: Resultsmentioning

confidence: 99%

“…[27] For cyclohexane, the general Amber FF (GAFF) for organic molecules[28] has been selected, since preliminary investigations showed that poor results were obtained in reproducing density with OPLS-AA. PMMA coordinates and topology were taken from a previous study,[29] using standard OPLS parameters. The hydrated (by means of TIP3P water molecules[30]) DOPC bilayer was modeled according to CHARMM FF[31], which is able to reproduce available experimental information on the structure and dynamics of phospholipid bilayers reasonably well.…”

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Computational study of the DPAP molecular rotor in various environments: from force field development to molecular dynamics simulations and spectroscopic calculations

Macchiagodena

Frate

Brancato

et al. 2017

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

Fluorescent molecular rotors (FMRs) belong to an important class of environment-sensitive dyes capable to act as nanoprobes to measure the viscosity and polarity of their microenvironment. FMRs have found widespread applications in various research fields, ranging from analytical to biochemical sciences, for example in intracellular imaging studies or in volatile organic compound detection. Here, a computational investigation of a recently proposed FMR, namely the 4-(diphenylamino)phthalonitrile (DPAP), in various chemical environments is presented. A purposely developed molecular mechanics force field is proposed and then applied to simulate the rotor into a high-and low-polar solvent (i.e., acetonitrile, tetrahydrofuran, o-xylene and cyclohexane), a polymer matrix and a lipid membrane. Subtle effects of the molecular interactions with the embedding medium, the structural fluctuations of the rotor and its rotational dynamics are analyzed in some detail. Results correlate with a previous work, thus supporting the reliability of the model, and provide further insights on the environment-specific properties of the dye. In particular, it is shown how molecular diffusion and rotational correlation times of the FMR are affected by the surrounding medium and how the molecular orientation of the dye becomes anisotropic once immersed in the lipid bilayer. Moreover, a qualitative correlation between the FMR rotational dynamics and the fluorescence lifetime is detected, a result in line with the observed viscosity dependence of its emission. Finally, optical absorption spectra are computed and successfully compared with their experimental counterparts.

show abstract

Section: Resultssupporting

confidence: 88%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Computational study of the DPAP molecular rotor in various environments: from force field development to molecular dynamics simulations and spectroscopic calculations

Macchiagodena

Frate

Brancato

et al. 2017

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

show abstract

“…When dispersed at low concentration in PMMA (i.e., 0.2 wt.‐%), compound 1a shows a fluorescence emission peaked at 540 nm with a Stokes shift of 90 nm, perfectly in agreement with results collected in solution. Compound 1a is a strong emitter also in the solid phase when dispersed in PMMA with Φ f slightly lower than that observed in solution (63 % against 68 %), despite the geometry constrains occurring in the glass matrix that prevent the dissipative phenomena potentially experienced in solution due to conformational changes . Above this concentration, the fluorescence band significantly changed its look and emission quenching occurred although only to a certain extent (from 63 % to 45 % at the highest 1a content).…”

Section: Resultsmentioning

confidence: 84%

Green/Yellow‐Emitting Conjugated Heterocyclic Fluorophores for Luminescent Solar Concentrators

et al. 2018

Self Cite

View full text Add to dashboard Cite

In this study, we report on the synthesis of new organic fluorophores containing either the benzo[1,2‐d:4,5‐d′]bisthiazole or the dithieno[3,2‐b:2′,3′‐d]silole heterocyclic unit, and on their application for the fabrication of luminescent solar concentrators (LSCs) made of poly(methyl methacrylate) (PMMA) thin films. In solution, the new compounds absorbed light in the visible region and displayed a brilliant green emission in the 500–600 nm range with moderate‐to‐good fluorescence quantum yields (0.25–0.68). Dispersions of selected fluorophores in PMMA thin films mostly maintained the light absorption features observed in solution, although in the case of benzobisthiazole‐based fluorophore 1a an evident fluorescence red‐shift was observed when increasing the compound concentration in the film. In agreement with its promising optical properties, LSCs prepared with the latter compound yielded interesting optical efficiencies up to 6.42 %, not far from those of state‐of‐the‐art PMMA LSC devices.

show abstract

“…BSA‐derived particles also have a high potential for controlled biodegradation by proteases at preprogramed rates, when released into the environment . Fluorescent‐dye labeled BSA‐particles can be versatile for sensing purposes and the presence of a large number of functional groups with different pKa values on the particle provides an excellent pH‐sensing platform, as demonstrated here . Particle surface can be readily modified with natural ligands, as shown here, to enhance cellular uptake.…”

Section: Introductionmentioning

confidence: 99%

White-Emitting Protein Nanoparticles for Cell-Entry and pH Sensing

Stromer

Kumar

2016

Adv. Funct. Mater.

View full text Add to dashboard Cite

Facile synthesis of white‐emitting, protein‐based, metal‐free, stable, nontoxic, and pH sensitive, advanced functional nanoparticles (GlowDots), as alternatives to quantum dots, is reported here. Controlled cross‐linking of bovine serum albumin resulted in facile formation of spherical nanoparticles of 35 nm in diameter with a sharp size distribution (±10 nm), which were then conjugated with specific dyes to produce white‐emitting particles with tunable excitation wavelengths. Chemical novelty is that the particle size, size distribution, stability, surface chemistry, and emission properties are under full chemical control where the size and absorption/emission properties are independently tuned. Up to 100 dye molecules were attached to each particle, on an average, and hence, particles acquired strong absorption cross‐sections as well as high brightness. White fluorescence of GlowDots is strongly sensitive to pH over a range of pH 2–11, and pH‐induced emission changes are fully reversible. The particles readily entered HeLa cells and emission color depended on particle location in the live cells, which is most likely due to the local environment surrounding the particles. These are the very first reports of white‐emitting advanced functional nanoparticles that are biodegradable, sensitive to pH, and amenable for live cell imaging to probe the subcellular compartments.

show abstract

Tuning of dye optical properties by environmental effects: a QM/MM and experimental study

Abstract: The present work is aimed at a deeper investigation of two recently synthesized heteroaromatic fluorophores by means of a computational multilayer approach, integrating quantum mechanics (QM) and molecular mechanics (MM).

Cited by 11 publications

References 48 publications

Computational study of the DPAP molecular rotor in various environments: from force field development to molecular dynamics simulations and spectroscopic calculations

Computational study of the DPAP molecular rotor in various environments: from force field development to molecular dynamics simulations and spectroscopic calculations

Green/Yellow‐Emitting Conjugated Heterocyclic Fluorophores for Luminescent Solar Concentrators

White-Emitting Protein Nanoparticles for Cell-Entry and pH Sensing

Contact Info

Product

Resources

About