Luminescence studies of polyelectrolyte behaviour in solution: 2. The application of steady-state fluorescence anisotropy measurements to the study of the conformational behaviour of poly(methacrylic acid) in dilute aqueous solution

Soutar, Ian; Swanson, Linda

doi:10.1016/0032-3861(94)90985-7

Cited by 17 publications

(13 citation statements)

References 24 publications

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“…[13][14][15] Fluorescence studies of polymethacrylic acid (PMAA) and polyacrylic acid (PAA) containing aromatic fluorescent probes such as naphthalene, anthracene and pyrene have been carried out by many authors to elucidate the properties of those polyelectrolytes in different solvents, pH, and surfactant addition. [16][17][18][19][20] Fluorescence anisotropy reflects the microviscosity and the solubilization dynamics of the probe molecule in solutions of polyelectrolytes. Reports in the literature using polarization and anisotropy of rhodamine 6 G in ethylene glycol demonstrate that the depolarization properties of the probe have relations with the solvent molecular alignment in jet flows.…”

Section: Introductionmentioning

confidence: 99%

Time resolved fluorescence anisotropy of basic dyes bound to poly(methacrylic acid) in solution

Oliveira¹,

Gehlen²

2003

J. Braz. Chem. Soc.

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Soluções de poli(ácido metacrílico) atático, PAMA com peso molecular na faixa de (1,6 a 3,4) x 10 5 g mol -1 , e com corantes fluorescentes 9-aminoacridina ou azul do nilo ligados à cadeia, foram estudados por medidas fotofísicas em função da viscosidade e polaridade do solvente. O comportamento dos segmentos da cadeia do PAMA nas vizinhanças da sonda fluorescente foi descrito pela mudança na rotação difusional dos corantes. O etilenoglicol expande a cadeia polimérica quando comparada com a forma mais compactada do corante-PAMA em 50% água/etilenoglicol. A variação do tempo de relaxação rotacional do corante ligado ao PAMA indica uma expansão progressiva da cadeia polimérica para uma forma aberta em etilenoglicol.Solutions of atactic poly(methacrylic acid), PMAA, with molecular weights in the range of (1.6 to 3.4) x 10 5 g mol -1 , and labeled with the fluorescent dyes 9-aminoacridine or Nile blue were studied by photophysical measurements as a function of solvent viscosity and polarity. The conformational behavior of the PMAA chain segments around the fluorescent probe was reported by the change in the rotational diffusion of the dyes. Ethylene glycol swells the polymer chain compared with the more contracted conformation of PMAA in 50% water/ethylene glycol. The change in the rotational relaxation time of the dye bound to PMAA with the decrease of water content in the solvent mixture indicates a progressive expansion of polymer chain to a more open coil form in solution.Keywords: dyes, polyelectrolytes, PMAA, rotational diffusion, solvent friction IntroductionPhotophysical studies of polymers in solution have been extensively reported in recent years. 1,2 Time resolved fluorescence spectroscopy (TRFS) was found to be particularly useful in the study of several types of polymers in solution, and in the presence of additives. 3-10 Time resolved anisotropy decay of a fluorescent probe attached to a polymer chain reflects the rotational relaxation of the probe, and the local dynamics of the polymer segments in solution. 2 The dependence of the segmental dynamics as a function solvent viscosity was studied by TRFS using anthracene attached to 1,2 polybutadiene. 11,12 The polymer local dynamics as well as the structural properties and relaxation processes of polymer and blends were studied by steady state and dynamic fluorescence using anthranyl and pyrenyl groups. [13][14][15] Fluorescence studies of polymethacrylic acid (PMAA) and polyacrylic acid (PAA) containing aromatic fluorescent probes such as naphthalene, anthracene and pyrene have been carried out by many authors to elucidate the properties of those polyelectrolytes in different solvents, pH, and surfactant addition. [16][17][18][19][20] Fluorescence anisotropy reflects the microviscosity and the solubilization dynamics of the probe molecule in solutions of polyelectrolytes. Reports in the literature using polarization and anisotropy of rhodamine 6 G in ethylene glycol demonstrate that the depolarization properties of the probe have relations with the solv...

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Section: Introductionmentioning

confidence: 99%

Time resolved fluorescence anisotropy of basic dyes bound to poly(methacrylic acid) in solution

Oliveira¹,

Gehlen²

2003

J. Braz. Chem. Soc.

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“…Time‐resolved fluorescence anisotropy measurements allow one to obtain both the size via the rotational diffusion of the molecule, as well as its segmental dynamics and steric restriction of motions . Figure A shows a characteristic anisotropy decay curve r ( t ) for dPGS‐ICC at 20 °C.…”

Section: Resultsmentioning

confidence: 99%

“…As we have recently shown, time‐resolved fluorescence spectroscopy can provide a powerful tool to analyze the structural flexibility and dynamics of polymeric nanoparticles . Using a fluorescent probe attached to the polymer scaffold, time‐resolved fluorescence anisotropy measurements allow one to obtain both the size, via the rotational diffusion of the molecule, as well as its segmental dynamics and steric restriction of motions . For instance, segmental dynamics of nanoparticle branches can be regarded as an important factor for the interaction affinity of dPGS in the cellular context.…”

Section: Introductionmentioning

confidence: 99%

Temperature and environment dependent dynamic properties of a dendritic polyglycerol sulfate

Boreham

Brodwolf

Pfaff

et al. 2014

Polymers for Advanced Techs

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Structural changes within dendritic polymer scaffolds may influence the polymer's behavior in biological relevant systems such as tissues and cells. A dendritic polyglycerol sulfate (dPGS) was recently found to act as an inhibitor of inflammatory processes. Here, we investigated the molecular dynamics and environmental sensitivity of dPGS using an indocarbocyanine (ICC) labeled variant (dPGS-ICC). The environmental sensitivity was demonstrated by UV/Vis and fluorescence spectroscopic characterization of dPGS-ICC in different solvents. In particular, fluorescence lifetime measurements revealed additional information on the local dye environment that manifest themselves in characteristic fluorescence lifetime signatures depending on the solvent. Furthermore, the interaction of dPGS-ICC with a model cell system-giant unilamellar vesicles (GUVs)-was studied with fluorescence lifetime imaging microscopy. We observed that dPGS-ICC is enriched in the membrane but does not penetrate into the lumen of the GUV. The characteristic lifetime signature of dPGS-ICC within the lipid membrane (τ mean = 1.6 ns) was clearly different from that obtained for dPGS-ICC in aqueous solution (τ mean = 0.42 ns) and can thus be employed to dissect differential interactions of dPGS in tissue. By using time-resolved fluorescence depolarization, we further showed that the size of dPGS shrinks by nearly 50% above 30°C. These results contribute to a further understanding of dPGS structure and dynamics and may help to provide tailor-made polymer architectures for biomedical applications.

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“…(This extrapolation procedure assumes proportionality between t c and h/T.) For example, this form of extrapolation for ACE-labeled PMAA at pH 12.7 using iodide as a quencher results in an r À1 o value of 8.7 [111]. This can be achieved by the addition of relatively small concentrations of a quencher capable of dynamically deactivating the excited state [110].…”

Section: Optical Properties Of Polyelectrolytesmentioning

confidence: 99%

Optical Properties of Polyelectrolytes

Swanson

2010

Photochemistry and Photophysics of Polymer Materials

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A polyelectrolyte can be defined as a macromolecule with ionizable repeat units, which can consequently display pH-dependent behavior when dissolved in aqueous solution.As the term polyelectrolyte can also be extended to encompass natural biopolymers, which contain ionizable groups such as peptides, proteins, and DNA, it is perhaps not surprising that synthetic polyelectrolytes are often used as simple models for more complex biological systems. Indeed, many of the photophyscial techniques discussed in this chapter were developed by biologists and biophysicists interested in the conformational behavior and interactions of biopolymers [1].

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Luminescence studies of polyelectrolyte behaviour in solution: 2. The application of steady-state fluorescence anisotropy measurements to the study of the conformational behaviour of poly(methacrylic acid) in dilute aqueous solution

Cited by 17 publications

References 24 publications

Time resolved fluorescence anisotropy of basic dyes bound to poly(methacrylic acid) in solution

Time resolved fluorescence anisotropy of basic dyes bound to poly(methacrylic acid) in solution

Temperature and environment dependent dynamic properties of a dendritic polyglycerol sulfate

Optical Properties of Polyelectrolytes

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