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In Situ Measurements of Polymer Micellization Kinetics with Millisecond Temporal Resolution.

ABSTRACT: Utilizing synchrotron small-angle X-ray scattering (SAXS) integrated with a microfluidic device, micellization kinetics of a diblock co-polymer, poly(ethylene glycol)-b-poly(caprolactone) (PEG-b-PCL) was measured in situ with millisecond temporal and micrometer spatial resolution. The evolutionary regimes of polymer micellization - nucleation, fusion, and insertion were directly observed. The five-inlet microfluidic device provided steady continuous mixing of the polymer solution and the antisolvent. Solvent replacement was mainly dominated by lateral diffusion across the hydrodynamically focused central layer, whose thickness could be precisely designed and manipulated from mass balance of the partitioning streams. Knowing the micellization kinetics of the polymers is essential for design and optimization of self-assembled polymeric nanostructures. The technique of integrating SAXS with microfluidic devices can be translatable to other systems for a breadth of applications.

SUBMITTER: Kalkowski J

PROVIDER: S-EPMC6777845 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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In Situ Measurements of Polymer Micellization Kinetics with Millisecond Temporal Resolution.

Kalkowski Joseph J Liu Chang C Leon-Plata Paola P Szymusiak Magdalena M Zhang Pin P Irving Thomas T Shang Weifeng W Bilsel Osman O Liu Ying Y

Macromolecules 20190415 9

Utilizing synchrotron small-angle X-ray scattering (SAXS) integrated with a microfluidic device, micellization kinetics of a diblock co-polymer, poly(ethylene glycol)-<i>b</i>-poly(caprolactone) (PEG-<i>b</i>-PCL) was measured in situ with millisecond temporal and micrometer spatial resolution. The evolutionary regimes of polymer micellization - nucleation, fusion, and insertion were directly observed. The five-inlet microfluidic device provided steady continuous mixing of the polymer solution a ...[more]

PMID: 31588150

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Project description:In-situ forming implants (ISFIs) represent a simple, tunable, and biodegradable polymer-based platform for long-acting drug delivery. However, drugs with different physicochemical properties and physical states in the polymer-solvent system exhibit different drug release kinetics. Although a few limited studies have been performed attempting to elucidate these effects, a large, systematic study has not been performed until now. The purpose of this study was to characterize the in vitro drug release of 12 different small molecule drugs with differing logP and pKa values from ISFIs. Drug release was compared with polymer degradation as measured by lactic acid (LA) release and change in poly(DL-lactide-co-glycolide) (PLGA) molecular weight (MW) measured by size exclusion chromatography with multi-angle laser light scattering (SEC-MALS). Drug physical state and morphology were also measured using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Together, these results demonstrated that hydrophilic drugs have higher burst release at 24 h (22.8-68.4%) and complete drug release within 60 days, while hydrophobic drugs have lower burst release at 24 h (1.8-18.9%) and can sustain drug release over 60-285 days. Overall, drug logP and drug physical state in the polymer-solvent system are the most important factors when predicting the drug release rate in an ISFI for small-molecule drugs. Hydrophilic drugs exhibit high initial burst and less sustained release due to their miscibility with the aqueous phase, while hydrophobic drugs have lower initial burst and more sustained release due to their affinity for the hydrophobic PLGA. Additionally, while hydrophilic drugs seem to accelerate the degradation of PLGA, hydrophobic drugs on the other hand seem to slow down the PLGA degradation process compared with placebo ISFIs. Furthermore, drugs that were in a crystalline state within the ISFI drugs exhibited more sustained release compared with amorphous drugs.

Dataset Information

In Situ Measurements of Polymer Micellization Kinetics with Millisecond Temporal Resolution.

Publications

In Situ Measurements of Polymer Micellization Kinetics with Millisecond Temporal Resolution.

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