Preferential excimer emission from amphiphilic alternating copolymers of 2-vinylnaphthalene and maleic acid in aqueous solution

Morishima, Yotaro; Kobayashi, Takaomi; Nozakura, Shun‐ichi; Webber, S. E.

doi:10.1021/ma00170a018

Cited by 32 publications

(23 citation statements)

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“…3,4, 12, 21-23), excimer formation (e.g., refs. [24][25][26][27][28][29][30][31][32], phosphorescence (19,(33)(34)(35), and fluorescence anisotropy (e.g., refs. 13, 3-3).…”

Section: Introductionmentioning

confidence: 99%

Luminescence studies of hydrophobically modified, water-soluble polymers. I. Fluorescence anisotropy and spectroscopic investigations of the conformational behaviour of copolymers of acrylic acid and styrene or methyl methacrylate

Ebdon¹,

Hunt²,

Lucas³

et al. 1995

Can. J. Chem.

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Fluorescence spectroscopy and anisotropy measurements have been used to study a series of styrene -acrylic acid, STY-AA, and methyl methacrylate -acrylic acid, MMA-AA, copolymers in dilute methanolic and aqueous solutions. Copolymerization of either STY or MMA with AA has little effect upon the rate of intramolecular segmental motion in methanol solutions. In aqueous media, intramolecular hydrophobic aggregation occurs and restricts the macromolecular dynamics to an extent dependent upon pH, nature of the comonomer, and copolymer composition. The hydrophobic domains formed in these copolymer systems can solubilize organic guests. In this respect, STY is a more powerful modifier of AA-based polymer behaviours than is MMA. In general, the hydrophobic modification increases the solubilization power of the resultant polymer. Furthermore, the copolymers retain their solubilization capacities to higher values of pH the more hydrophobic the comonomer and the greater its content in the copolymer. The interiors of the hydrophobic aggregates reduce the mobilities of occluded guests: the microviscosities of the domain interiors depend upon the nature of the hydrophobe, pH, and copolymer composition.

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“…3,4, 12, 21-23), excimer formation (e.g., refs. [24][25][26][27][28][29][30][31][32], phosphorescence (19,(33)(34)(35), and fluorescence anisotropy (e.g., refs. 13, 3-3).…”

Section: Introductionmentioning

confidence: 99%

Luminescence studies of hydrophobically modified, water-soluble polymers. I. Fluorescence anisotropy and spectroscopic investigations of the conformational behaviour of copolymers of acrylic acid and styrene or methyl methacrylate

Ebdon¹,

Hunt²,

Lucas³

et al. 1995

Can. J. Chem.

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“…A third strategy has involved increasing the label content such that the luminescent species itself acts as a modifier, which subsequently creates a new class of fluorescent polyelectrolyte [20,[27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42]. Copolymers of this type, containing a high degree of aromaticity have shown potential as media for efficient light harvesting OPTICAL PROPERTIES OF POLYELECTROLYTES (i.e.…”

Section: Probes and Labelsmentioning

confidence: 99%

“…Because poly(carboxylic acid)s have received particular attention in the literature in respect of their fluorescence behavior in aqueous solution [6,12,13,[16][17][18][19][20][21][22][23][24]26,[29][30][31][32][33][34][43][44][45][46] and have been comprehensively studied by classical methods [2][3][4][47][48][49][50][51][52] , this important class of polyelectrolyte will be reviewed initially before moving on to other examples. The active repeat unit in poly(methacrylic acid) (PMAA) is the carboxylic acid function, which dissociates upon increasing pH to form negatively charged carboxylate anions.…”

Section: Homopolymersmentioning

confidence: 99%

“…The complexity observed in polymer fluorescence decay kinetics is further exacerbated when fluorescent polyelectrolytes are dissolved in aqueous media [29,30,33,35,37,43,120,122,[128][129][130][131][132]: segregation of the macromolecular structure into hydrophobic and hydrophilic-rich domains results in differing degrees of water penetration which further complicates the time-resolved fluorescence [26]. Within this context, more recent attempts to describe time-resolved polymer photophysical data include use of the "blob model" [133,134], which accounts for the range of environments encountered in heterogeneous systems by invoking a distribution of rate constants for excimer formation.…”

Section: Excimer Formationmentioning

confidence: 99%

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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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“…Various types of amphiphilic polyelectrolytes have been synthesized so far, including random copolymers (19,20,(22)(23)(24)(25)(26), block copolymers (27)(28)(29)(30), and alternating copolymers (31)(32)(33)(34)(35)(36)(37). The sequence distribution of charged and hydrophobic units along the polymer chain is an important structural factor to determine whether the hydrophobic self-association is an intra-or intermolecular event.…”

mentioning

confidence: 99%

Spectroscopic Characterization of Unimer Micelles of Hydrophobically Modified Polysulfonates

Morishima

1995

Multidimensional Spectroscopy of Polymers

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Polysulfonates modified with bulky hydrophobic groups of cyclic structure form unimolecular micelles (unimers) in aqueous solution owing to intramolecular self-organization. This chapter deals with the characterization of the unimers of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and hydrophobic methacrylamides carrying cyclododecyl, 1-adamantyl, or 1-naphthylmethyl substituent group, by light scattering, small-angle X-ray scattering, fluorescence, NMR, and IR techniques. The absence of intermolecular association is indicated by the absence of non-radiative energy transfer from naphthalene to pyrene which are labeled respectively on the individual polymer molecules. Light scattering studies show that the unimers have extremely large ratios of mass to dimension indicating an extremely compact conformation. Local motions of the hydrophobes in the unimers are highly restricted as indicated by 1 H-NMR relaxation times. FTIR indicates that hydrogen bonding between the spacer amide bonds contributes to the stabilization of the compact unimer structure.Amphiphilic polymers, a class of water-soluble polymers consisting of both hydrophobic and hydrophilic segments in a polymer chain, have a tendency to selforganize in aqueous solution. Water molecules surrounding the hydrophobes in the amphiphilic polymers in aqueous solution form an ice-like structure (7) because the water molecules tend to form the largest possible number of hydrogen bonds on the surface of the hydrophobes. The hydrophobes would associate such that they have the smallest possible area of contact with the aqueous phase by releasing the structured water molecules into free water. The principal driving force for this hydrophobic association is a large increase in entropy which is sufficient to overcome a positive enthalpy change due to the breakup of the hydrogen bonds (2,5). The hydrophobic association is the main cause for the self-organization of amphiphilic polymers in aqueous solution.In amphiphilic polyelectrolytes, the hydrophobic interaction competes with electrostatic repulsion. Therefore, the balance of the contents of the hydrophobes and charged segments in the polymers are a critical factor to determine whether or not the self-organization occurs. For example, amphiphilic polycarboxylic acids, which adopt an extended chain conformation at high pH, would collapse to form compact conformation upon decreasing pH (4-9). This transition from an extended to a compact 0097-6156/95/0598-0490$13.75/0

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Preferential excimer emission from amphiphilic alternating copolymers of 2-vinylnaphthalene and maleic acid in aqueous solution

Cited by 32 publications

References 14 publications

Luminescence studies of hydrophobically modified, water-soluble polymers. I. Fluorescence anisotropy and spectroscopic investigations of the conformational behaviour of copolymers of acrylic acid and styrene or methyl methacrylate

Luminescence studies of hydrophobically modified, water-soluble polymers. I. Fluorescence anisotropy and spectroscopic investigations of the conformational behaviour of copolymers of acrylic acid and styrene or methyl methacrylate

Optical Properties of Polyelectrolytes

Spectroscopic Characterization of Unimer Micelles of Hydrophobically Modified Polysulfonates

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