Structural Characterization of Glycoconjugate Polystyrene in Aqueous Solution

Wataoka, Isao; Urakawa, Hiroshi; Kobayashi, Kazukiyo; Akaike, Toshihiro; Schmidt, Manfred; Kajiwara, Kanji

doi:10.1021/ma9809132

Cited by 56 publications

(54 citation statements)

References 18 publications

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“…Most bottle-brush macromolecules investigated so far were synthezised via the grafting-through method and had rather stiff, bulky side chains based on poly styrene ͑PS͒, 1-9 poly͑methyl methacrylate͒ ͑PMMA͒, 10 poly-2-vinylpiridine, 11 or maltopentaose 12 which were grafted to a rather stiff PS backbone 4,[6][7][8][9]12 or poly͑alkyl methacrylate͒ ͑PAMA͒ backbone.…”

Section: Introductionmentioning

confidence: 99%

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On the shape of bottle-brush macromolecules: Systematic variation of architectural parameters

Rathgeber

Pakuła

Wilk

et al. 2005

The Journal of Chemical Physics

214

346

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We measured the form factor of bottle-brush macromolecules under good solvent conditions with small-angle neutron scattering and static light scattering. The systems under investigation are brushes, synthesized via the grafting-from route, built from a poly͑alkyl methacrylate͒ backbone to which poly͑n-butyl acrylate͒ side chains are densely grafted. The aim of our work is to study how the systematic variation of structural parameters such as the side chain length and backbone length change the conformation of the polymer brushes in solution. All spectra can be consistently described by a model, considering the bottle-brush polymers as flexible rods with internal density fluctuations. Parameters discussed are ͑1͒ the contour length per main chain monomer l b , ͑2͒ the fractal dimension of the side chains D s , as well as ͑3͒ the fractal dimension D, and ͑4͒ the Kuhn length k of the overall brush. l b = 0.253± 0.008 nm is found to be independent of the side chain length and equal to the value found for the bare main chain, indicating a strongly stretched conformation for the backbone due to the presence of the side chains. The fractal dimension of the side chains is determined to be D s = 1.75± 0.07 which is very close to the value of 1 / 0.588Ϸ 1.70 expected for a three-dimensional self-avoiding random walk ͑3D-SAW͒ under good solvent conditions. On larger length scales the overall brush appears to be a 3D-SAW itself ͑D = 1.64± 0.08͒ with a Kuhn-step length of k = 70± 4 nm. The value is independent of the side chain length and 46 times larger than the Kuhn length of the bare backbone ͑ k = 1.8± 0.2 nm͒. The ratio of Kuhn length to brush diameter k / d ജ 20 determines whether lyotropic behavior can be expected or not. Since longer side chains do not lead to more persistent structures, k / d decreases from 8 to 4 with increasing side chain length and lyotropic behavior becomes unlikely.

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Section: Introductionmentioning

confidence: 99%

“…1, 3, 5, 10-12, and 14͒ and static light scattering ͑SLS͒ ͑Refs. 1, 3,5,6,[8][9][10][11][12], and 15͒ experiments on the fractionated or in combination with gel permeation chromatography ͑GPC͒ on the eluted samples. Small-angle scattering experiments with neutrons ͑SANS͒ ͑Ref.…”

Section: Introductionmentioning

confidence: 99%

On the shape of bottle-brush macromolecules: Systematic variation of architectural parameters

Rathgeber

Pakuła

Wilk

et al. 2005

The Journal of Chemical Physics

214

346

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“…6 In an earlier work, we have reported the structure of glycopolymer composed of a polystyrene backbone with pentamaltose side chains in aqueous solution. 7 Here the small-angle X-ray scattering indicated the glycopolymer as represented by a cylinder with one or two broken points, and its backbone was found to assume a large cross-sectional pseudo-helix. Since the side chains are not long enough to fill the space along the extended hydrophobic backbone, the backbone is thought to assume a large helical conformation in order to cover its surface with hydrophilic side chains.…”

mentioning

confidence: 88%

“…A similar tendency was observed in the toluene solutions of polymacromonomers of lower degrees of polymerization. 7 The increase of the degree of polymerization in a molecular model results in the change of the scattering profile mainly in the small q region ( Figure 7). However, the overall shape becomes more marked as a cylinder than an ellipsoid as the degree of polymerization increases.…”

Section: Molecular Mode/mentioning

confidence: 99%

Molecular Specification of Homopolymer of Vinylbenzyl-Lactose-Amide in Aqueous Solution

Wataoka

Urakawa

Kobayashi

et al. 1999

Polym J

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ABSTRACT:The lactose-carrying polystyrene derivative, PYLA, is known as the material suitable for the incubation of liver cells and for drug delivery systems. PYLA was dissolved in 0.1 M urea aqueous solution, and its structure was analyzed from the results of small-angle X-ray scattering and the molecular modeling. PYLA was found to have the shape of a molecular bottle brush in solution, composed of a large pseudo helix of polystyrene backbone. The amphiphilic nature of the backbone and side chains is thought to determine the backbone conformation.KEY WORDS Small-Angle X-Ray Scattering I Polymacromonomer I Glycopolymer I Lactose I Recent advance in the precise polymerization technique has resulted in synthesizing many novel functional polymers, most of which mimic biopolymers. Those novel polymers are often found to be physiologically more active than the corresponding biopolymers. Thus in future, those novel materials are expected to compose a major biomedical system including cell separation, cell culture, drug delivery agent, and artificial antigen. Hybrids of synthetic polymers and biopolymers are of a particular interest, since the hybrid may enhance the characteristics of parent polymers. Carbohydrate is one of the most important candidates as a ligand or recognition signal, and a series of glycoconjugate polystyrene derivatives have been synthesized with varying the types of a pendant oligosaccharides. Here a convenient synthetic route 1 was developed to construct the amphiphilic structure by arranging hydrophobic polystyrene main chains and hydrophilic pendant oligosaccharides. Synthesized glycoconjugate polymers were in fact found to function as a highly sensitive ligand. Highly concentrated multiantennary glyco signals along the hydrophobic main chains enhance the interaction with various types of carbohydrate-binding proteins. The enhancement is also attributed to the presence of the hydrophobic phenyl groups, although its active role is not clearly understood. 2 The glycoconjugate polystyrene derivative is a type of comb-shaped polymers termed as polymacromonomers, where relatively long branches pendant from the backbone chain with a regular interval. An extensive research effort has been focused to prepare densely grafted polymacromonomers by radical polymerization. Although the monomer is a high molecular weight precursor composed of almost monodisperse polymers t To whom correspondence should be addressed. 590(or oligomers) with a vinyl end group, the radical polymerization results in polydisperse polymacromonomers. The living radical polymerization is an alternative route to prepare polymacromonomers with less polydispersity, but the molecular weight cannot be expected so high as in the conventional radical polymerization.Small-angle X-ray and light scattering revealed a bottlebrush-like cylindrical shape representing the polymacromonomer composed of a polymethacrylate backbone with oligostyrene side chains in toluene solution. 3 • 4 The polymethacrylate backbone seems to be obliged to take an e...

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“…For example, polystyrenes having -lactoside appendages still have excellent water solubility. In these glycoclusters, the flexible nature of the polymer main chain permits its structural rearrangement and therefore, these glycoclusters take unique cylindrical structures composed of hydrophobic cores and hydrophilic surfaces [47][48][49]. As a result, hydrophobic moieties interact with each other in an intrapolymer fashion, and intermolecular interactions to induce polymer aggregates are highly limited.…”

Section: Water Solubility Of the Cellulose Derivativesmentioning

confidence: 99%

Cellulose Chemistry Meets Click Chemistry: Syntheses and Properties of Cellulose-Based Glycoclusters with High Structural Homogeneity

et al. 2011

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-1,4-Glucans having oligosaccharide appendages (O-/N-linked -maltoside and O-/N-linked -lactoside) at 6C positions of all repeating units can be readily prepared from cellulose through a two step strategy composed of: (1) regio-selective and quantitative bromination/azidation to afford 6-azido-6-deoxycellulose; and (2) the subsequent Cu + -catalyzed coupling with oligosaccharides having terminal alkyne. The resultant cellulose derivatives showed improved water solubility in comparison to native cellulose; they, however, bound to carbohydrate-binding proteins in a rather non-specific manner. Molecular dynamics calculations revealed that these properties are attributable to rigid sheet-like structures of the cellulose derivatives and the subsequent exposure of their hydrophobic moieties to solvents.

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Structural Characterization of Glycoconjugate Polystyrene in Aqueous Solution

Cited by 56 publications

References 18 publications

On the shape of bottle-brush macromolecules: Systematic variation of architectural parameters

On the shape of bottle-brush macromolecules: Systematic variation of architectural parameters

Molecular Specification of Homopolymer of Vinylbenzyl-Lactose-Amide in Aqueous Solution

Cellulose Chemistry Meets Click Chemistry: Syntheses and Properties of Cellulose-Based Glycoclusters with High Structural Homogeneity

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