Polymer-Grafted Nanoparticle Membranes with Controllable Free Volume

Bilchak, Connor; Buenning, Eileen; Asai, M.; Zhang, Kai; Durning, C. J.; Kumar, Sanat K.; Huang, Yucheng; Benicewicz, Brian C.; Gidley, David W.; Cheng, Shiwang; Sokolov, Alexei P.; Minelli, Matteo; Doghieri, Ferruccio

doi:10.1021/acs.macromol.7b01428

Cited by 102 publications

(161 citation statements)

References 48 publications

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“…The immobilization of the AuNPs on the surface is supported by the fact that particle spacing is not affected (within experimental error) by subsequent thermal annealing (see Figure S6, Supporting Information). It has been reported that higher free volume can be achieved in PGNPs than in a melt of free polymer chains due to packing constraints . This indicates that simple geometric arguments that rely on constant density cannot be used to describe PGNP scaling.…”

Section: Resultsmentioning

confidence: 99%

Scaling Laws for Polymer Chains Grafted onto Nanoparticles

Yang

Kim

Wang

et al. 2018

Macro Chemistry & Physics

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An experimental approach is presented for identifying the scaling laws for polymer chains grafted onto gold nanoparticles. Poly(ethylene oxide) of various molecular weights are grafted onto gold nanoparticles via thiol end‐functional groups. The polymer‐grafted nanoparticles are self‐assembled into monolayers from solvents of different quality. Over a significant range of graft densities, nanoparticle monolayers deposited from good (athermal) solvent exhibit particle spacing that scales according to theoretical predictions for chains in dilute solution. This unexpected result for ordered nanoparticle monolayers is discussed in the context of the deposition process. In monolayers deposited from theta solvent, molecular weight scaling of particle spacing breaks down, possibly due to chain length dependence of solvent quality. In poor solvent, the structure of nanoparticle assemblies is not sufficiently ordered to obtain reliable measurements, possibly due to loss of nanoparticle dispersion. This approach opens up the possibility for accurate measurement of the effect of solvent on grafted chain scaling in nanoparticle assemblies.

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Section: Resultsmentioning

confidence: 99%

Scaling Laws for Polymer Chains Grafted onto Nanoparticles

Yang

Kim

Wang

et al. 2018

Macro Chemistry & Physics

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“…To illustrate the sasPDF method we have applied it to some representative nanoparticle assemblies from the literature (Nykypanchuk et al, 2008;Han et al, 2008;Bilchak et al, 2017). The first example is from DNA-templated gold nanoparticle superlattices, originally reported by Nykypanchuk et al (2008).…”

Section: Application To Representative Structuresmentioning

confidence: 99%

“…The molecular weight and density of the capping polymers can be varied and in the current sample were 0.47 chains nm À2 and 132 kDa, respectively. Studies had suggested that similar NPA samples exhibit no structural order, on the basis of an empirical metric using the height of the first peak in the measured SðQÞ (Bilchak et al, 2017). Here we apply the sasPDF method to obtain a more complete understanding of the structure of this NPA.…”

Section: Tablementioning

confidence: 99%

SASPDF: pair distribution function analysis of nanoparticle assemblies from small-angle scattering data

Liu

Janke

et al. 2020

J Appl Crystallogr

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sasPDF, a method for characterizing the structure of nanoparticle assemblies (NPAs), is presented. The method is an extension of the atomic pair distribution function (PDF) analysis to the small-angle scattering (SAS) regime. The PDFgetS3 software package for computing the PDF from SAS data is also presented. An application of the sasPDF method to characterize structures of representative NPA samples with different levels of structural order is then demonstrated. The sasPDF method quantitatively yields information such as structure, disorder and crystallite sizes of ordered NPA samples. The method was also used to successfully model the data from a disordered NPA sample. The sasPDF method offers the possibility of more quantitative characterizations of NPA structures for a wide class of samples.

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“…Polymer-grafted solid or porous core particles are investigated with great interest for their use in adsorption [1], separation devices [2] and as components of hybrid membranes [3][4][5]. These hybrid particles can be packed into porous beds and they combine the intrinsic properties of the core particles and of the polymers grafted on them [6].…”

Section: Introductionmentioning

confidence: 99%

Thermally triggered on demand permeability of hybrid silica beds made of packed thermoresponsive organo-silica microparticles

Jadhav¹,

Spalletta²,

Scalarone³

2019

Express Polym. Lett.

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This work reports the preparation and testing of porous beds made from packed vinylated silica microparticles (SiMPs) grafted with thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) and exhibiting on demand thermally triggered permeability. PNIPAM-grafted hybrid SiMPs with diameters of 1.40-1.55 µm were synthesized and characterized with Attenuated Total Reflection Fourier Transform Infrared Spetroscopy (ATR-FTIR), Thermogravimetric Analysis (TGA), Flow Particle Image Analysis (FPIA) and Scannning Electron Miscroscopy (SEM) to elucidate their composition and morphology. The PNIPAM-grafted SiMPs were used to prepare thermoresponsive beds of dimensions 1×0.5×0.5 cm inside filtration tubes. The thermo-regulated permeability of solutions of selected model compounds, namely caffeine, ketoprofen, orange II, bromocresol green and cresol red across the hybrid beds was tested by calculating the retention percentage of the model compounds at temperatures below and above the lower critical solution temperature (LCST) of PNIPAM. The results showed a clear control over the permeability of the packed hybrid beds mediated by external temperature changes. This control was achieved by virtue of the switchable nanovalves created by the thermoresponsive PNIPAM present in the inter-particle voids of the packed beds.

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Polymer-Grafted Nanoparticle Membranes with Controllable Free Volume

Cited by 102 publications

References 48 publications

Scaling Laws for Polymer Chains Grafted onto Nanoparticles

Scaling Laws for Polymer Chains Grafted onto Nanoparticles

SASPDF: pair distribution function analysis of nanoparticle assemblies from small-angle scattering data

Thermally triggered on demand permeability of hybrid silica beds made of packed thermoresponsive organo-silica microparticles

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