Purity of double hydrophilic block copolymers revealed by capillary electrophoresis in the critical conditions

Sutton, Adam T.; Read, Emmanuelle; Maniego, Alison R.; Thevarajah, Joel J.; Marty, Jean‐Daniel; Destarac, Mathias; Gaborieau, Marianne; Castignolles, Patrice

doi:10.1016/j.chroma.2014.10.105

Cited by 17 publications

(31 citation statements)

References 73 publications

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“…Only a handful of techniques can measure the absolute molecular mass distribution [3]. The gold standard is size exclusion chromatography (SEC) using universal calibration [4], which does not always work [5,6]. New techniques must be developed to aid in the advancement of polymer science.…”

Section: Introductionmentioning

confidence: 99%

Scaling exponent and dispersity of polymers in solution by diffusion NMR

Williamson

Röding

Miklavcic

et al. 2017

Journal of Colloid and Interface Science

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Molecular mass distribution measurements by pulsed gradient spin echo nuclear magnetic resonance (PGSE NMR) spectroscopy currently require prior knowledge of scaling parameters to convert from polymer self-diffusion coefficient to molecular mass. Reversing the problem, we utilize the scaling relation as prior knowledge to uncover the scaling exponent from within the PGSE data. Thus, the scaling exponent-a measure of polymer conformation and solvent quality-and the dispersity (M w /M n ) are obtainable from one simple PGSE experiment. The method utilizes constraints and parametric distribution models in a two-step fitting routine involving first the mass-weighted signal and second the number-weighted signal. The method is developed using lognormal and gamma distribution models and tested on experimental PGSE attenuation of the terminal methylene signal and on the sum of all methylene signals of polyethylene glycol in D 2 O. Scaling exponent and dispersity estimates agree with known values in the majority of instances, leading to the potential application of the method to polymers for which characterization is not possible with alternative techniques. Keywords:Pulsed gradient spin echo, pulsed field gradient, Nuclear Magnetic Resonance spectroscopy, Molecular weight distribution, Polymers, DOSY, Polydispersity Index, Self-diffusion, Molar mass, Flory exponent, Lognormal distribution, Gamma distribution, End-group analysis, Scaling law Synthetic polymers have distributions of molecular masses determined by their synthesis [1]. Measuring the molecular mass distribution rather than its average is important because the dispersity can influence polymer properties [2]. Absolute as opposed to relative measurements are needed when using polymer physics to fully realize the potential applications of a polymer [3]. Only a handful of techniques can measure the absolute molecular mass distribution [3]. The gold standard is size exclusion chromatography (SEC) using universal calibration [4], which does not always work [5,6]. New techniques must be developed to aid in the advancement of polymer science.Pulsed gradient spin echo nuclear magnetic resonance (PGSE NMR) [7,8] is a powerful technique for obtaining the distribution of polymer self-diffusion coefficients D [9], from which the distribution of molecular masses M can be obtained by the scaling law [10] ration give PGSE NMR a competitive edge with respect to SEC. Chemical shift information [7], e.g. in a diffusion ordered spectroscopy (DOSY) plot [11], provides the ability to observe chemical heterogeneity and impurity. Sample preparation generally does not require filtration because contaminates from large particles such as dust do not impact the experiment. However, the scaling parameters of Eq. (1) specific to that polymersolvent system must be found by measuring ⟨D⟩ on fractionated samples of the polymer with known M. Therefore, currently all PGSE NMR-based methods which convert from D to M cannot independently measure the absolute molecular mass distribution [...

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Section: Introductionmentioning

confidence: 99%

Scaling exponent and dispersity of polymers in solution by diffusion NMR

Williamson

Röding

Miklavcic

et al. 2017

Journal of Colloid and Interface Science

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“…Further, the analysis of sugars in breakfast cereals involved injecting samples with particles of breakfast cereal samples precipitated in water 8 . This also extends to the analysis of branched polyelectrolytes or copolymers 12,13 . Extensive work has also been completed in the development of CE techniques specifically for the analysis of proteins for proteomics 14 , chiral separation of natural or synthetic peptides 15 and microchip separations of proteins and peptides 16 .…”

Section: Introductionmentioning

confidence: 71%

Capillary Electrophoresis to Monitor Peptide Grafting onto Chitosan Films in Real Time

Thevarajah

O’Connor

Castignolles

et al. 2016

JoVE

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Free-solution capillary electrophoresis (CE) separates analytes, generally charged compounds in solution through the application of an electric field. Compared to other analytical separation techniques, such as chromatography, CE is cheap, robust and effectively requires no sample preparation (for a number of complex natural matrices or polymeric samples). CE is fast and can be used to follow the evolution of mixtures in real time (e.g., chemical reaction kinetics), as the signals observed for the separated compounds are directly proportional to their quantity in solution. Here, the efficiency of CE is demonstrated for monitoring the covalent grafting of peptides onto chitosan films for subsequent biomedical applications. Chitosan's antimicrobial and biocompatible properties make it an attractive material for biomedical applications such as cell growth substrates. Covalently grafting the peptide RGDS (arginine - glycine - aspartic acid - serine) onto the surface of chitosan films aims at improving cell attachment. Historically, chromatography and amino acid analysis have been used to provide a direct measurement of the amount of grafted peptide. However, the fast separation and absence of sample preparation provided by CE enables equally accurate yet real-time monitoring of the peptide grafting process. CE is able to separate and quantify the different components of the reaction mixture: the (non-grafted) peptide and the chemical coupling agents. In this way the use of CE results in improved films for downstream applications. The chitosan films were characterized through solid-state NMR (nuclear magnetic resonance) spectroscopy. This technique is more time-consuming and cannot be applied in real time, but yields a direct measurement of the peptide and thus validates the CE technique.

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“…The zeta potentials of all nanoparticles were greater than +30 mV, indicating the particles are cationic and stable in solution. Cationic polymers are notoriously difficult to characterize, and copolymers are even more problematic . Size exclusion chromatography (SEC) was not used due to difficulties preventing polymer adsorption to the SEC stationary phase, and to the lack of appropriate cationic standards .…”

Section: Resultsmentioning

confidence: 99%

Performance and selectivity of cationic nanoparticle pseudo‐stationary phases in electrokinetic chromatography

et al. 2016

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Electrokinetic chromatography (EKC) is a powerful analytical technique that uses an ionic pseudo-stationary phase (PSP) to separate neutral compounds. Although anionic surfactants are the most common choice for PSP, cationic latex nanoparticles are an attractive alternative. Reversible addition-fragmentation chain transfer (RAFT) polymerization was used to synthesize several types of diblock copolymers that self-assemble into latex nanoparticles, which were characterized by a variety of techniques including diffusion NMR. The performance of each nanoparticle as a PSP was studied by using a homologous series of ketones and linear solvation energy relationships (LSER) analysis. A cationic homopolymer coating was found to be necessary to prevent band broadening caused by analyte interactions with nanoparticles adsorbed to the capillary surface. No significant difference in methylene selectivity or LSER parameters was observed between nanoparticles with different cationic shells, but differences were observed between nanoparticles with different hydrophobic cores. Cationic latex nanoparticles behaved more like anionic latex nanoparticles than like cationic surfactants, suggesting that selectivity is primarily driven by the hydrophobic portion of a PSP. Cationic latex nanoparticles in combination with a homopolymer cationic capillary coating are an excellent choice for EKC analyses where an anodic electroosmotic flow is required.

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Purity of double hydrophilic block copolymers revealed by capillary electrophoresis in the critical conditions

Cited by 17 publications

References 73 publications

Scaling exponent and dispersity of polymers in solution by diffusion NMR

Scaling exponent and dispersity of polymers in solution by diffusion NMR

Capillary Electrophoresis to Monitor Peptide Grafting onto Chitosan Films in Real Time

Performance and selectivity of cationic nanoparticle pseudo‐stationary phases in electrokinetic chromatography

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