preparation-highly-porous-coordination-polymer-coatings-on

Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous ...

E. O. Lawrence Berkeley National Laboratory

The 3D structure of three individual aggregates composed of 165 nm polystyrene primary particles is revealed nondestructively by hard X-ray phase-contrast synchrotron nanotomography. Three-dimensional image analysis allows us for the first time to obtain the complex inner porosity of the entire aggregate. It is demonstrated that despite their rather compact structure, characterized by a fractal dimension equal to 2.7, the produced aggregates are still porous, with porosity increasing with its size. Generated pores have diameters from 100 nm to 3 μm and are almost completely interconnected.

Quantification of a single aggregate inner porosity and pore accessibility using hard X-ray phase-contrast nanotomography.

The effect of polymeric surfactants, copolymers of n-butyl acrylate (BA) and acrylic acid (AA), on shear-induced gelation of a colloidal system in the absence of additional electrolytes is studied. One random (PBA-co-PAA) and two block copolymer (PBA-b-PAA, with different PAA lengths) surfactants have been synthesized by ATRP and used in this work. The colloidal system is composed of strawberry-like particles with a rubbery core, partially covered by a few grafted plastic patches. In the absence of any surfactant, as the colloidal system passes through a microchannel at a Peclet number of 220 and a particle volume fraction of 0.15, shear-induced gelation occurs and the particles coalesce partially, due to the rubbery core, leading to a fractal dimension of the clusters constituting the gel equal to 2.78. On the other hand, in the presence of any of the three polymeric surfactants, shear-induced gelation occurs only in the range of low surfactant surface density. Meanwhile, the fractal dimension of the clusters decreases with adsorption of the two block surfactants, reaching a plateau value of about 2.58, while for the random surfactant it remains constant and equal to 2.78, like in the absence of any surfactant. This indicates that adsorption of the block surfactants can reduce the particle coalescence, while adsorption of the random surfactant cannot. Moreover, for all three surfactants, as their surface density increases progressively, a transition from solid-like gel to a liquid-like state occurs and finally no shear-induced gelation or even aggregation occurs. Since the three surfactants comprise carboxylic groups, considering also the results in the literature (Zaccone et al., J. Phys. Chem. B, 2008, 112, 1976; 6793), we can reach a general conclusion that carboxylic groups on the particle surface not only stabilize the particles through electrostatic repulsion, but also generate very short-range, strongly repulsive (e.g. hydration, steric) forces, which when high enough protect the particles from intense shear-activated aggregation.

Shear-induced gelation of soft strawberry-like particles in the presence of polymeric P(BA-b-AA) surfactants.

By combining elements from colloidal and polymer reaction engineering a new approach toward macroporous, mechanically robust polymer particles is presented, which does not require any porogenic additives. Specifically, aggregation and breakage in turbulent conditions of aggregates originating from fully destabilized primary latex particles is applied to produce compact, micrometer-sized clusters. Post-polymerization of monomer introduced initially to swell the primary particles is imparting mechanical rigidity and permanence to the internal structure. The resulting microclusters exhibit an internal porosity on the order of 70% and relatively broad pore size distribution, with exceptionally large pores, ranging from about 50 nm to 10 μm in diameter. These particulate microclusters, produced via reactive gelation under shear, are fractal objects with fractal dimension around 2.7, as opposed to the more open fractal structure of a monolith produced via stagnant reactive gelation, with fractal dimension of 1.9. Such macroporous particles are thought to be useful in applications requiring pores on the micrometer scale, e.g., in the chromatography of biomolecules or for packing beds perfusive to convective flow.

Synthesis of macroporous polymer particles using reactive gelation under shear.

Reactive gelation under shear is a recently developed procedure toward rigid macroporous polymeric particles that does not require the use of any porogen. A comprehensive study of the effect of individual parameters on the resulting material characteristics is presented. Primary particle properties are found to be pivotal, namely, the primary particles size, cross-linking degree, and outer shell composition. Operating parameters also play a significant role; specifically, the effects of applied shear rate, salt feeding rate, swelling degree of primary particles, waiting time before postpolymerization, and postpolymerization temperature are investigated. By varying the operating conditions, the size, internal structure, as well as porosity of the fabricated microclusters may be controlled. The pores are invariably micrometer-sized, with pore size distributions exhibiting adjustable maxima. Thanks to the sequential character of the procedure, different parameters may be tuned individually at different stages along the preparation route, allowing thus for high versatility in the control of different properties of the final material.

Macroporous polymer particles via reactive gelation under shear: effect of primary particle properties and operating parameters.

In this work, novel macro-porous chromatographic stationary phases, combining low mass transfer resistance and high binding capacity, were thoroughly characterized in terms of porosity, HETP, resolution and binding capacity. These new stationary phases exhibited better performance compared to commercially available materials, i.e. Poros 50HS and Fractogel EMD SO3 (M). With the technique of reactive gelation under shear, it is possible to produce particles with pores from 100 nm to several microns, in which part of the flow can go through. This way, the mass transport inside the particles is significantly increased with perfusive flow faction values between 0.02 and 0.01. Despite the low pore surface area resulting from the large pore size, high binding capacity is obtained by functionalizing the pore surface with charged polymeric brushes resulting in a binding capacity in the range from 25 to 140 mg/mL col. This, together with the high mass transfer, gives excellent resolution performance and dynamic binding capacity compared to other commercial materials even at high flow rates.

Perfusive ion-exchange chromatographic materials with high capacity.

A macroporous particulate support prepared previously by reactive gelation under shear and functionalized with poly(N-isopropylacrylamide), PNIPAM, brushes of variable length is applied for temperature-responsive chromatography, whereby temperature modulates hydrophobic interactions. Several different analytes, including small pharmaceuticals, peptides, proteins and monoclonal antibodies are employed. Contrary to the most commonly observed behavior in conventional chromatography, increasing retention is observed at elevated temperatures. Peak broadening is quantified using the peak standard deviation, which depends on both the polymer chain conformation and analyte adsorptivity. The favorable effect of grafted polymer thickness on retention becomes progressively less pronounced for thicker grafted PNIPAM layers. The effect of eluent composition on solute-sorbent interactions was investigated by introducing NaCl, methanol, dioxane and by varying the pH. Salt or organic solvent addition affects apart from the analytes solution properties, the hydrophobicity of the stationary phase itself. Frontal analyses performed at different temperatures to determine dynamic binding capacities, indicate small mass transfer resistances imposed by this novel packing material.

Article	Year
Quantification of a single aggregate inner porosity and pore accessibility using hard X-ray phase-contrast nanotomography. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 21939251	2011
Shear-induced gelation of soft strawberry-like particles in the presence of polymeric P(BA-b-AA) surfactants. Physical chemistry chemical physics : PCCP\| PubMed ID: 23011512	2012
Synthesis of macroporous polymer particles using reactive gelation under shear. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 24853641	2014
Macroporous polymer particles via reactive gelation under shear: effect of primary particle properties and operating parameters. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 25354173	2014
Perfusive ion-exchange chromatographic materials with high capacity. Journal of chromatography. A\| PubMed ID: 25498557	2014
Application of polymeric macroporous supports for temperature-responsive chromatography of pharmaceuticals. Journal of chromatography. A\| PubMed ID: 26150252	2015

Alexandros Lamprou

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