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Energy and electron transfer processes in polymeric nanoparticles

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Abstract

We report herein a study on photoinduced electron transfer (eT) and energy transfer (ET) processes occurring between 9-methylanthracene-acrylate (A) and N,N-dimethylaniline-acrylate (D) derivatives incorporated into polymeric nanoparticles (NP). Five types of NPs were synthesized: PAD0, PAD25, PAD75, PD25, and PD75. All NPs are composed of a crosslinked polymer matrix of methyl methacrylate and ethylene glycol dimethacrylate. In addition, PAD0, PAD25 and PAD75 contain low doping levels of A. For PAD25 and PAD75, 25% and 75% of the mole fraction of methyl methacrylate is replaced by D, respectively. PD25 and PD75 were prepared as above but without A. NPs (diameter 6-9 nm) dispersed in organic solvents were characterized based on their UV-visible absorption, emission, excitation, and excitation anisotropy spectra and time dependent absorption and emission spectroscopy techniques. The emission decay profiles of A and D were always complex. Results indicate that A senses two distinct environments in all NPs. The emission quenching of PAD0 by DMA in DCM solutions is dynamic, and it is apparent that a significant fraction of A is inaccessible to the quencher. The emission of A is efficiently quenched by the presence of D in PAD25 and PAD75. The intra-NP photoinduced eT quenching mechanism has static and dynamic components. Selective excitation of D in PAD25 and PAD75 leads to the formation of the excited state of A via a singlet-singlet ET Föster type mechanism. Results indicate that both intra-NP eT and ET processes are more efficient in PAD75 due to the reduced average D*-A separation in these NPs.

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Abbreviations

A:

9-Methylanthracene-acrylate derivative (9-anthracenylmethyl methacrylate) incorporated into the polymeric nanoparticles

α i :

The corresponding amplitude of the ith component of the multiexponential decay

D:

N,N-Dimethylaniline-acrylate derivative (N-(4-dimethylamino-benzyl)-2-methyl-acrylamide) incorporated into the polymeric nanoparticles

DCM:

Dichloromethane

DLS:

Dynamic light scattering

EGDMA:

Ethylene glycol dimethacrylate

EI method:

The lifetime’s distribution analysis software provided by Edinburgh Instruments

eT:

Electron transfer process

ET:

Energy transfer process

k q :

Quenching rate constant

K SV :

Stern-Volmer rate constant

9-MA:

9-Methylanthracene

MMA:

Methyl methacrylate

NPs:

Nanoparticles

PAD0:

NP composed of a crosslinked polymer matrix of methyl methacrylate, ethylene glycol dimethacrylate and a low doping level of A

PAD25:

NP composed of a crosslinked polymer matrix of methyl methacrylate, ethylene glycol dimethacrylate, D and a low doping level of A. 25% of the mole fraction of methyl methacrylate (relative to PAD0) is replaced by D

PAD75:

NP composed of a crosslinked polymer matrix of methyl methacrylate and ethylene glycol dimethacrylate, D and a low doping level of A. 75% of the mole fraction of methyl methacrylate (relative to PAD0) is replaced by D

PD25:

NP composed of a crosslinked polymer matrix of methyl methacrylate, ethylene glycol dimethacrylate and D. 25% of the mole fraction of methyl methacrylate (relative to PAD0) is replaced by D

PD75:

NP composed of a crosslinked polymer matrix of methyl methacrylate, ethylene glycol dimethacrylate and D. 75% of the mole fraction of methyl methacrylate (relative to PAD0) is replaced by D

PeT:

Photoinduced electron transfer process

r:

Excitation steady-state anisotropy spectrum

R 0 :

Critical distance for the Föster resonance ET process

R AD :

Radius of the sphere of action (Perrin’s model)

RW:

Relative weight

TCSPC instrument:

Time-correlated single-photon counting fluorometer

THF:

Tetrahydrofuran

TRES:

Time resolved emission spectrum

V:

Volume of the sphere of action (Perrin’s model)

α i :

Opulation of fluorophores characterized by an emission lifetime τi in the continuous distribution of the lifetime model assumed by the EI method

τ:

Fluorescence lifetime

τ M :

Mean fluorescence lifetime

Φ ET :

Efficiency for energy transfer

ϕ f :

Fluorescence quantum yield

σ:

Standard deviation of a Gaussian distribution

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Authors and Affiliations

  1. Departamento de Química, Facultad de Ciencias Exactas, Físico-Químicas y Naturales, Universidad Nacional de Río Cuarto, 5800, Río Cuarto, Argentina

    Claudia Solis, Juan J. Torres, Natalia Gsponer, Carlos Previtali, Rodrigo Palacios, Hernán Montejano & Carlos Chesta

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  1. Claudia Solis
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  2. Juan J. Torres
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  3. Natalia Gsponer
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Correspondence to Carlos Chesta.

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Electronic supplementary information (ESI) available. See DOI: 10.1039/c3pp50183c

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Solis, C., Torres, J.J., Gsponer, N. et al. Energy and electron transfer processes in polymeric nanoparticles. Photochem Photobiol Sci 12, 2146–2159 (2013). https://doi.org/10.1039/c3pp50183c

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