Adsorption of soft NIPAM nanogels at hydrophobic and hydrophilic interfaces: Conformation of the interfacial layers determined by neutron reflectivity

Liu, Pengfei; Freeley, Mark; Zarbakhsh, Ali; Resmini, Marina

doi:10.1016/j.jcis.2022.05.010

Cited by 7 publications

(3 citation statements)

References 78 publications

(84 reference statements)

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“…This result is somewhat counterintuitive, as characterization of the NGs indicated that NG 5 -tBAEMA-3 presented the lowest surface charge. However, NGs with less crosslinked matrices have been shown to possess higher flexibility and adaptability to interfaces [ 22 , 55 ]. The crosslinker, once incorporated in the matrix, does not impact toxicity on its own, as previously reported [ 16 ].…”

Section: Resultsmentioning

confidence: 99%

“…The relationship between the formulation and properties of NGs has attracted considerable research, particularly given the importance of chemical structure and morphology in influencing the interaction with biological entities, in vivo, resulting in a protein/biomolecular corona [ 21 ]. We investigated the impact of changes in formulations and structure on the interfacial behavior of N -isopropylacrylamide (NIPAM) NGs, using a combination of neutron reflectivity and atomic force microscopy [ 22 ], and correlated formulations with changes in thermoresponsive properties [ 23 ], together with the role of monomer reactivities [ 24 ]. More recently, we reported our results on the role that charges play on biocorona formation with acrylamide-based NGs [ 25 ].…”

Section: Introductionmentioning

confidence: 99%

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The Role of Crosslinker Content of Positively Charged NIPAM Nanogels on the In Vivo Toxicity in Zebrafish

et al. 2023

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Polymeric nanogels as drug delivery systems offer great advantages, such as high encapsulation capacity and easily tailored formulations; however, data on biocompatibility are still limited. We synthesized N-isopropylacrylamide nanogels, with crosslinker content between 5 and 20 mol%, functionalized with different positively charged co-monomers, and investigated the in vivo toxicity in zebrafish. Our results show that the chemical structure of the basic unit impacts the toxicity profile depending on the degree of ionization and hydrogen bonding capability. When the degree of crosslinking of the polymer was altered, from 5 mol% to 20 mol%, the distribution of the positively charged monomer 2-tert-butylaminoethyl methacrylate was significantly altered, leading to higher surface charges for the more rigid nanogels (20 mol% crosslinker), which resulted in >80% survival rate (48 h, up to 0.5 mg/mL), while the more flexible polymers (5 mol% crosslinker) led to 0% survival rate (48 h, up to 0.5 mg/mL). These data show the importance of tailoring both chemical composition and rigidity of the formulation to minimize toxicity and demonstrate that using surface charge data to guide the design of nanogels for drug delivery may be insufficient.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Role of Crosslinker Content of Positively Charged NIPAM Nanogels on the In Vivo Toxicity in Zebrafish

et al. 2023

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“…This polymer has been discussed and implemented for numerous applications (Lanzalaco and Armelin, 2017;Bilardo et al, 2022). Besides, it has been the object of research in numerous studies-both experimental (Rizzi et al, 2021;Vdovchenko et al, 2021;Liu et al, 2022) and computational (Pang et al, 2010;Bruce et al, 2019;García and Hasse, 2019). We chose to simulate a 20-mer of PNIPAM, since it is long enough to show a Coil-Globule transition, while not being unnecessarily long.…”

Section: Model System Poly(n-isopropylacrylamide)mentioning

confidence: 99%

Water model determines thermosensitive and physicochemical properties of poly(N-isopropylacrylamide) in molecular simulations

Quoika

Kamenik²,

Fernández‐Quintero³

et al. 2023

Front. Mater.

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Poly (N-isopropylacrylamide) (PNIPAM) is a famous representative of thermosensitive polymers. Thermosensitive polymers undergo a phase transition with lower critical solution temperature. Commonly, their phase behavior is linked to a conformational collapse above a certain temperature. This thermosensitive conformational transition is called Coil-Globule transition. In contrast, most other polymers usually show inverse temperature behavior, i.e., an upper critical solution temperature, corresponding to a Globule-Coil transition. Besides their numerous possible applications, thermosensitive polymers are of interest for fundamental research, because of similarities to macromolecular conformational transitions, e.g., protein folding. The counter-intuitive behavior of thermosensitive polymers is commonly associated with solvation effects. Thus, an accurate description of the solvent is crucial for the investigation of thermosensitive polymers in molecular simulations. Here, we investigate the influence of the in silico water model on the thermosensitive Coil-Globule transition in molecular dynamics simulations. To this end, we performed extensive atomistic simulations of the syndiotactic PNIPAM 20-mer at multiple temperatures with eight different water models–four of which are 3-point water models (TIP3P-type) and four are 4-point water models (TIP4P-type). We found that the thermosensitive Coil-Globule transition is strongly influenced by the water model in the simulations. Depending on the water model, the conformational ensemble of the polymer is shifted significantly, which leads to dramatically different results: The estimated transition temperature may span between 255 and 350 K. Consequently, depending on the description of the solvent, the physicochemical and mechanical properties of these polymers, e.g., the polymer-solvent affinity and persistence length, vary. These divergent results originate from the strength of interactions between polymer and solvent, but also on the bulk state of the solvent. Both these quantities vary between water models. We found that the Lennard-Jones interaction parameter ϵ of the water model correlates with the transition temperature of the polymer. Indeed, the quadrupole moment of the water model shows an even higher correlation with this quantity. Our results suggest a connection between the phase diagram of the solvent and the thermosensitive transition of the polymer.

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Temperature/pH/reduction-sensitive multiple stimulus-responsive nanogels synthesized by one-pot method for design as curcumin carriers

Cai,

Zhong,

Huang

et al. 2024

European Polymer Journal

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Adsorption of soft NIPAM nanogels at hydrophobic and hydrophilic interfaces: Conformation of the interfacial layers determined by neutron reflectivity

Cited by 7 publications

References 78 publications

The Role of Crosslinker Content of Positively Charged NIPAM Nanogels on the In Vivo Toxicity in Zebrafish

The Role of Crosslinker Content of Positively Charged NIPAM Nanogels on the In Vivo Toxicity in Zebrafish

Water model determines thermosensitive and physicochemical properties of poly(N-isopropylacrylamide) in molecular simulations

Temperature/pH/reduction-sensitive multiple stimulus-responsive nanogels synthesized by one-pot method for design as curcumin carriers

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