Networking Properties of Cyclodextrin-Based Cross-Linked Polymers Probed by Inelastic Light-Scattering Experiments

Rossi, Barbara; Caponi, Silvia; Castiglione, Francesca; Corezzi, S.; Fontana, A.; Giarola, Marco; Mariotto, G.; Mele, Andrea; Petrillo, C.; Trotta, Francesco; Viliani, G.

doi:10.1021/jp302047u

Cited by 59 publications

(120 citation statements)

References 36 publications

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“…Without exception, available results are all in agreement [3,4,[13][14][15][16][17][18][19][20][21][22]: the BP shifts towards higher frequencies and decreases in intensity when the sample becomes stiffer (increase of elastic constants). Recently, it has been proposed to quantitatively test the role played by the changes in the elastic properties by scaling the BP data with the Debye frequency, a quantity defined by the elastic medium.…”

Section: Introductionsupporting

confidence: 59%

Stress-Induced Modification of the Boson Peak Scaling Behavior

et al. 2013

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The scaling behavior of the so-called boson peak in glass-formers and its relation to the elastic properties of the system remains a source of controversy. Here, the boson peak in a binary reactive mixture is measured by Raman scattering (i) on cooling the unreacted mixture well below its glass transition temperature and (ii) after quenching to very low temperature the mixture at different times during isothermal polymerization. These different paths to the glassy phase are able to generate glasses with different amounts of residual stresses, as evidenced by the departure of the elastic moduli from a Cauchy-like relationship. We find that the scaling behavior of the boson peak with the properties of the elastic medium -as measured by the Debye frequency -holds for states in which the system is able to release internal stress and breaks down in the presence of residual stresses. These findings provide new insight into the boson peak behavior and are able to reconcile the apparently conflicting results presented in literature.

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Section: Introductionsupporting

confidence: 59%

Stress-Induced Modification of the Boson Peak Scaling Behavior

et al. 2013

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“…Here we simply wish to stress that primary hydroxy groups are mainly involved in the formation of a network as shown by FTIR–ATR, Raman and solid-state NMR analyses [15]. Moreover, the elastic properties of cyclodextrin nanosponges were determined by analysis of the spectral modification of the Boson peak and Brillouin frequency [16]. Using ultrasound-assisted synthesis and a suitable cross-linker molar ratio, spherical nanosponges of submicron size were obtained [17].…”

Section: Reviewmentioning

confidence: 99%

Cyclodextrin-based nanosponges as drug carriers

Trotta¹,

Zanetti²,

Cavalli³

2012

Beilstein J. Org. Chem.

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SummaryCyclodextrin-based nanosponges, which are proposed as a new nanosized delivery system, are innovative cross-linked cyclodextrin polymers nanostructured within a three-dimensional network. This type of cyclodextrin polymer can form porous insoluble nanoparticles with a crystalline or amorphous structure and spherical shape or swelling properties. The polarity and dimension of the polymer mesh can be easily tuned by varying the type of cross-linker and degree of cross-linking. Nanosponge functionalisation for site-specific targeting can be achieved by conjugating various ligands on their surface. They are a safe and biodegradable material with negligible toxicity on cell cultures and are well-tolerated after injection in mice. Cyclodextrin-based nanosponges can form complexes with different types of lipophilic or hydrophilic molecules. The release of the entrapped molecules can be varied by modifying the structure to achieve prolonged release kinetics or a faster release. The nanosponges could be used to improve the aqueous solubility of poorly water-soluble molecules, protect degradable substances, obtain sustained delivery systems or design innovative drug carriers for nanomedicine.

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“…[23][24][25] Nanosponges have been shown to be promising nanoporous materials with interesting properties of sorption of both organic and inorganic molecular species. [29][30][31][32][33] In addition, the controlled ability to undergo modifications from the state of a rigid gel to liquid suspension has been recently evidenced in CDNS-based hydrogels by changing the hydration level of polymers in water. 21,22,28 Besides their potential practical applications, nanosponges are interesting model systems for the study of water-swollen cross-linked polymers.…”

Section: Introductionmentioning

confidence: 99%

Water and polymer dynamics in a model polysaccharide hydrogel: the role of hydrophobic/hydrophilic balance

Rossi

Venuti

D’Amico

et al. 2015

Phys. Chem. Chem. Phys.

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The molecular dynamics of water and a polymer matrix is here explored in a paradigmatic model of a polysaccharide hydrogel, by the combined use of UV Raman scattering and infrared measurements. The case example of cyclodextrin nanosponges (CDNS)/hydrogel is chosen since the simultaneous presence in the structure of the polymer matrix of both hydrophilic and hydrophobic sites mimics the complexity of polysaccharide hydrogels. In this way, the contributions provided by the balance between the hydrophilicity/hydrophobicity and the grade of entanglement of the polymer hydrogel to lead to the formation of the gel phase are separately accounted and evaluated. As main results, we found that the hydrophobic CH groups inserted on the aromatic ring of CDNS experience a more pronounced dynamic perturbation with respect to the carbonyl groups due to the collision between the solvent and vibrating atoms of the polymer. The overall results provide a detailed molecular picture of the swelling phenomena occurring when a chemically cross-linked polymer contacts with water or biological fluids and exploits the potentiality of UV Raman spectroscopy to retrieve dynamic information besides their structural counterpart obtained by the classical analysis of the basic features of vibrational spectra.

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Networking Properties of Cyclodextrin-Based Cross-Linked Polymers Probed by Inelastic Light-Scattering Experiments

Cited by 59 publications

References 36 publications

Stress-Induced Modification of the Boson Peak Scaling Behavior

Stress-Induced Modification of the Boson Peak Scaling Behavior

Cyclodextrin-based nanosponges as drug carriers

Water and polymer dynamics in a model polysaccharide hydrogel: the role of hydrophobic/hydrophilic balance

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