Molecularly imprinted macroporous polymer monolithic layers for L-phenylalanine recognition in complex biological fluids

In present work, the development of macroporous monolithic layers bearing the artificial recognition sites toward L-phenylalanine has been carried out. The set of macroporous poly(2-aminoethyl methacrylate-co-2-hydroxyethyl methacrylate-co-ethylene glycol dimethacrylate) materials with average pore size ranged in 340–1200 nm was synthesized. The applicability of Hildebrand's and Hansen's theories for the prediction of polymer compatibility with porogenic solvents was evaluated. The dependences of average pore size on theoretically calculated parameters were plotted. The linear trend detected for Hansen's theory has indicated the high suitability of this approach to select appropriate porogens. The synthesized monolithic MIP layers were tested toward the ability to rebind phenylalanine-derivative in microarray format. The influence of such factors as average pore size of the material, the concentration of template molecule in polymerization mixture, interaction time of analyte with its imprinted sites on binding efficiency were studied. The developed materials demonstrated good analyte rebinding from buffer solution with recognition factors 2.5–3.4 depending on the MIP sample. The comparable rebinding efficiency was also detected when the analysis was carried using complex biological media. The selectivity of phenylalanine binding from the equimolar mixture of structural analogues was 81.9% for free amino acid and 91.2% for labeled one.     

Effect of porogenic solvent on the porous properties of polymer monoliths

Polymer monoliths with open pores and median pore size of about 15 nm–3 μm have been successfully synthesized by photoinitiated polymerization of butyl methacrylate and ethylene glycol dimethacrylate monomers. The solubility of the monomers in a porogenic solvent is determined by Hildebrand solubility parameter, and it is found that it has great effect on the pore size of the polymers synthesized. Polymers with larger pores are usually generated with poorer solvents for the monomers. However, polymers with different pore sizes and porosities have been obtained using porogenic solvents with similar Hildebrand solubility parameters. The evaporation rate of the porogenic solvents might be another critical factor affecting the properties of the polymer monoliths. Moreover, the effect of water as a cosolvent on the pore size and porosity of the polymers have also been investigated. Polymers with larger pore size have been prepared with the presence of water due to the occurrence of earlier phase separation in the polymerization. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Pore structure control of macroporous methylsilsesquioxane monoliths prepared by in situ two-step processing

Macroporous methylsilsesquioxane (MSQ) monoliths have been prepared by in situ two-step processing using an initial acid catalysis step accompanied by an epoxide-mediated condensation step in the presence of ammonium chloride (NH₄Cl). We investigate the effects of duration time of acidic step, heat-treatment and hydrothermal treatment on the macroporous morphology and pore structures of MSQ monoliths. The duration time of acidic step gives an important effect on the macroporous morphology and pore structures of MSQ monoliths, resulting from the polymerization of MSQ. Heat-treatment and hydrothermal treatment basically do not spoil the macroporous morphology of MSQ monoliths, while obviously varies the mesopore/micropore structures including pore size, pore volume, and pore size distribution. The macroporous MSQ materials with thick skeleton and intrinsic hydrophobicity are promising for wide applications such as ultra performance liquid chromatography (UPLC), superhydrophobic materials and so on.     

Applicability of the two-dimensional approach to polymer miscibility in pure and mixed organic liquids

Previously it was proposed that the solvent power of a pure or mixed organic liquid for a given polymer can be characterized by two parameters δ_h and χ_H. Using these two parameters, a two-dimensional (2D) solubility diagram can be constructed to predict solubility or insolubility. In the investigation only the polymers, poly(methyl methacrylate), polystyrene, and poly(vinyl acetate), were used to demonstrate the applicability of the 2D method. In this note, applicability of the 2D method to the 33 polymers investigated in Hansen's works is presented.     

Compatibility studies with blends based on poly(n‐butyl methacrylate) and polyacrylonitrile

In this study, poly(n‐butyl methacrylate) (PBMA) was prepared by a suspension polymerization process, and blending with polyacrylonitrile (PAN) in N,N‐dimethyl acetamide to prepare PAN/PBMA blends in various proportions. Hansen's three dimensional solubility parameters of PAN and PBMA were calculated approximately through the contributions of the structural groups. The compatibility in these blend systems was studied with theoretical calculations as well as experimental measurements. Viscometric methods, Fourier transform infrared spectroscopy, dynamic mechanical analysis, scanning electron microscopy, and thermogravimetric analysis were used for this investigation. All the results showed that a partial compatibility existed in PAN/PBMA blend system, which may be due to the intermolecular interactions between the two polymers. And, the adsorption experiment results showed that the addition of PBMA contributed to the enhancing adsorptive properties of blend fibers, which lays the foundation for further studying PAN/PBMA blend fibers with adsorptive function. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of solubility parameter difference between monomer and porogen on structures of poly (acrylonitrile–styrene-divinylbenzene) resins

In this work, the acrylonitrile (AN)-styrene (St)-divinylbenzene (DVB) resin was synthesized via suspension polymerization in the presence of inert porogens as diluent. The relationship of the solubility parameter (SP) of the materials and the porous properties of the resin was investigated. These porous spherical resin particles (0.25–0.84 mm) can be used as precursors of amidoxime resin which has a high metal ion chelating efficiency. The results showed that the porous properties (surface area and mean pore width) of the resin changed with variation in the compatibility between monomers and porogens. According to the the BET theory to N₂ sorption and scanning electron microscopy (SEM), the specific surface area of the obtained beads was strongly dependent on the compatibility of the components of the system and achieved values from 3.3 to 66.8 m²/g. The surface area of the terpolymer beads was found to rise with a decrease in the content of acrylonitrile or an increase in the SP of the porogens. However, the variation of the pore size was just the opposite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46979.     

Calculating hansen solubility parameters of polymers with genetic algorithms

In materials engineering, it is often essential to know what are the best solvents to process any polymer, and employing methods based on Hansen solubility parameters are an effective way to find them. In this work the Hansen solubility parameters of polyether sulfone, lignin, and bitumen have been calculated by an alternative optimization procedure. It has been shown that, by applying an evolutionary strategy to Hansen's correlation method, it is possible to improve the fitting of solubility spheres. Compared with previous calculations, most quality‐of‐fit parameters are optimized. As a result, the sphere radii are reduced and, except for lignin, at least one of the solubility parameters is considerably changed (by 0.9–1.5 MPa^1/2). Shortcomings of the correlation method are also pointed out, such as lack of data quality evaluation on set of solvents and uncertain character for partially solving solvents. At least the former could be handled by a proposed parameter called fill factor. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39696.     

Polymeric monolithic materials: Syntheses, properties, functionalization and applications

The synthetic particularities for the synthesis of polymer-based monolithic materials are summarized. In this context, monoliths prepared via thermal-, UV- or electron-beam triggered free radical polymerization, controlled TEMPO-mediated radical polymerization, polyaddition, polycondensation as well as living ring-opening metathesis polymerization (ROMP) will be covered. Particular attention is devoted to the aspects of controlling pore sizes, pore volumes and pore size distributions as well as functionalization of these supports. Finally, selected, recent applications in separation science, (bio-) catalysis and chip technology will be summarized.     

Polymer miscibility in organic solvents and in plasticizers—a two-dimensional approach

From thermodynamic considerations based on associated solution models and from the Hansen's three-dimensional solubility parameter concept, it is found that the solvent power of an organic liquid for a given polymer can be characterized by two parameters, δ_h and χ_H, where δ_h is the hydrogen-bonding solubility parameter of the liquid, and χ_H is a term which takes account of the dispersion and polar interactions between the liquid and the polymer and of the effects due to temperature and molecular size of the liquid. It is also found that Hansen's solubility sphere for the polymer can be represented as a solubility circle in the proposed χ_H^?δ_h plane. The proposed approach is applied successfully to polymer–plasticizer systems.     

Influence of Topology of Highly Porous Methacrylate Polymers on their Mechanical Properties

Porous polymer monoliths are prepared using glycidyl methacrylate and methyl methacrylate as monomers, in both cases crosslinked with ethylene glycol dimethacrylate. Up to 75% porous samples are produced using either emulsion templating or bulk polymerization with porogens. In the case of emulsion templating, a cellular topology with cavities between 3.1 and 5.5 µm is observed for both monomers, while a cauliflower‐like topology is formed in the case of bulk polymerization. The influence of topology features of monoliths on the mechanical properties is studied and for both polymers a dramatic influence, on both compressive moduli and compressive strength, is found. The mechanical parameters, namely elastic modulus and compressive strength are significantly higher for emulsion templated samples.     

Controlling porous properties of polymer monoliths synthesized by photoinitiated polymerization

Porous monoliths have been successfully prepared by photoinitiated polymerization of hydroxyethyl methacrylate and ethylene glycol dimethacrylate monomers in a porogenic solvent. By varying the composition of the starting solutions such as initiator fraction, monomer ratio and pore generator (porogen) fraction and type, as well as UV intensity, monoliths have been obtained with narrow pore size distribution and median pore size from about a few nanometres to a few micrometres. © 2012 Society of Chemical Industry     

Preparation and application of partially porous poly(styrene‐divinylbenzene) particles for lipase immobilization

Partially porous poly(styrene‐divinylbenzene) (PS‐DVB) particles in the micron size range were prepared by the method of multistep swelling and polymerization involving the use of polymeric porogens. Polystyrene (PS) seeds prepared by dispersion polymerization were expanded in particle size by absorbing styrene and initiator, and then polymerized to form polymeric porogen particles. The newly synthesized PS chains served as the porogens of the PS‐DVB particles, resulting from the copolymerization of styrene and divinylbenzene in the swollen polymeric porogen particles. PS‐DVB particles with a specific surface area of up to 34 m²/g and a pore volume of up to 0.15 cm³/g were obtained. The average pore diameter of PS‐DVB particles was in the range of 15–24 nm. An increasing amount of toluene used in the copolymerization step increased the pore volume and specific surface area. Lipase from Candida rugosa was immobilized on the prepared PS‐DVB by physical adsorption. The optimum temperature for enzymatic activity was increased and the thermal deactivation of enzyme in organic solvent was slowed down by the immobilization. However, compared with soluble enzyme, the immobilized lipase on PS‐DVB retained a less activity after the first stage deactivation, suggesting a possible change in the conformation of enzyme molecule by immobilization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 39–46, 2001     

Hydrophilic methacrylate monoliths as platforms for protein microarray

Hydrophilic macroporous monolithic materials based on a copolymer of 2-hydroxyethyl methacrylate with glycerol dimethacrylate was synthesized by photo-initiated free-radical polymerization of monomers in a presence of the low molecular mass porogens, such as cyclohexanol, dodecanol, toluene and heptane, as well as the solutions of hydrophobic polymers, namely, polystyrene of different molecular weights and concentrations in toluene, and poly(dimethyl siloxane) in heptane. The Hildebrand solubility parameters were used to predict the diluent-polymer compatibility. Pore size distribution and surface area characterization have been assessed by mercury intrusion porosimetry; scanning electron microscopy was used to evaluate the differences in macroporous morphology obtained with different porogenic agents. The monolithic materials were covalently attached to a glass surface directly at polymerization step. Monolithic layers were applied as platforms for microarrays to accomplish highly sensitive solid-phase protein analysis. The efficiency of developed microarrays was demonstrated using mouse IgG and goat anti-mouse IgG as a model affinity pair.     

A novel approach to the interpretation and prediction of solvent effects in the synthesis of macroporous polymers

A trivariate interpolation technique, the modified Shepard's method, was applied for the first time to explain and predict various properties of macroporous polymers from the Hansen solubility parameters of the porogens employed for polymerization. Highly crosslinked polymers and copolymers were prepared from ethylene glycol dimethacrylate and methacrylic acid by free‐radical polymerization with 30 different porogenic solvents. Instead of the spherical model used by Hansen, detailed three‐dimensional maps were computed to represent the measured properties in a δ_d–δ_p–δ_h diagram (where δ_d, δ_p, and δ_h are the Hansen solubility parameters according to the three types of bonding forces: dispersion, polar, and hydrogen‐bonding, respectively). This method was able to detect unapparent correlations between the different polymer properties, thus providing a better understanding of the pore‐formation process. An important finding was the crucial role of the initiator solubility and its partitioning between the solution and the polymer surface, which proved to be key factors for the explanation of many contradictory solvent effects. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Solubility parameter of a polyester composite material

The solubility parameters of a BMC composite material, its polyester matrix, and its low profile additive [poly(vinyl acetate)] were determined by using several methods. For Hildebrand's solubility parameter : calculation from molar additive laws and determination from unrelaxed elastic constants, these latter being determined from the propagation rate of ultrasonic waves. For partial solubility parameters from sorption test in saturated solvent atmosphere, using bidimensional solubility maps. The effect of glass fibers and mineral fillers on solvent absorption can be considered negligible. In contrast, the presence of the low profile additive significantly modifies the solubility parameter values. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2663–2671, 1998     

Prediction of plasticizer solvency using hansen solubility parameters

The solvating strength of a plasticizer for poly(vinyl chloride) resin is a measure of the interactive forces between these two materials. Hansen's three-dimensional solubility parameters provide a quantitative measure of these interactive forces. By using CO-ACT^SM service, a computer program designed for solvent systems with various resins, plasticizers were found to lie near the edge of the solvency “sphere” of PVC. The relative positions of various plasticizer structures are in the expected order, while known solvents show strong association and lubricating additives fall outside the solvency sphere of PVC.     

Preparation of macroporous methacrylate monolithic material with convective flow properties for bioseparation: Investigating the kinetics of pore formation and hydrodynamic performance

The preparation of macroporous methacrylate monolithic material with controlled pore structures can be carried out in an unstirred mould through careful and precise control of the polymerisation kinetics and parameters. Contemporary synthesis conditions of methacrylate monolithic polymers are based on existing polymerisation schemes without an in-depth understanding of the dynamics of pore structure and formation. This leads to poor performance in polymer usage thereby affecting final product recovery and purity, retention time, productivity and process economics. The unique porosity of methacrylate monolithic polymer which propels its usage in many industrial applications can be controlled easily during its preparation. Control of the kinetics of the overall process through changes in reaction time, temperature and overall composition such as cross-linker and initiator contents allow the fine tuning of the macroporous structure and provide an understanding of the mechanism of pore formation within the unstirred mould. The significant effect of temperature of the reaction kinetics serves as an effectual means to control and optimise the pore structure and allows the preparation of polymers with different pore size distributions from the same composition of the polymerisation mixture. Increasing the concentration of the cross-linking monomer affects the composition of the final monoliths and also decreases the average pore size as a result of pre-mature formation of highly cross-linked globules with a reduced propensity to coalesce. The choice and concentration of porogen solvent is also imperative. Different porogens and porogen mixtures present different pore structure output. Example, larger pores are obtained in a poor solvent due to early phase separation.     

Carbon Isotope Separation by Absorptive Distillation

Abstract

The feasibility of separating carbon isotopes by absorptive distillation has been studied for CO absorption by cryogenic solvents. Phase equilibrium, isotopic separation, and mass transfer data were taken between 77.4 and 114.3 K for the following solvents: propane, propylene, 1:1 propane-propylene, 1-butene, isobutane and nitrogen.

Carbon monoxide solubility followed Henry's Law, with a maximum experimental solubility of 6.5 mole per cent. Isotopic separation between CO in the gas and liquid phases using hydrocarbon solvents was several times that for pure CO vapor-liquid equilibrium. The maximum observed isotopic separation factor was 1.029 at 77.4 K with the propane-propylene solvent mixture. Mass transfer measurements yielded calculated HTU's of 2 to 5 cm for a possible separation system.

An attempt has been made to correlate isotopic separation data using Hildebrand's theory of solutions. The differential absorption of isotopic CO species is expressed as a difference in solubility of the isotopic CO molecules. Data for propane, propylene, and 1-butene show approximately the same behavior at varying temperatures.     

Critical analysis of the graphical determination of hansen's solubility parameters for lightly crosslinked polymers

The most widely accepted method for determining Hansen's three-dimensional solubility parameters (3DSP) for crosslinked polymers entails graphically estimating the center of a spherical region in 3DSP-coordinate space whose boundaries are defined in terms of the extent of swelling by solvents whose 3DSP values are known. In this article, the results of immersion tests performed at 25°C with 53 solvents on each of four commercial polymeric glove materials are used to critically evaluate this method. Analyses reveal a number of serious shortcomings with respect to the reliability of 3DSP estimates obtained. In the context of modeling solubility or other measures of solvent–polymer compatability, it is recommended that alternative methods be sought for determining 3DSPs for crosslinked polymers. © 1996 John Wiley & Sons, Inc.     

Poly(2-hydroxyethyl acrylate-co-ethyleneglycol dimethacrylate) monoliths synthesized by radiation polymerization in a mold

Copolymer monoliths of diethyleneglycol dimethacrylate and 2-hydroxyethyl-acrylate were prepared by using the advantage of radiation initiated polymerization over the thermally initiated polymerization, namely, that it is sufficient to use only a monomer and a porogenic solvent and no initiator is needed. Besides, the reaction can take place at any desired temperature in a mold of suitable size and shape.The results showed that increase of the HEA content in the comonomer mixture (up to 18 vol%) resulted in monoliths with increased pore size and hydrophilic character. The specific surface area of these monoliths was in the order of 1 m²/g. The porous properties could be fine-tuned by changing the solvent.Flow rate measurements for several eluents indicated that these monoliths could be useful as chromatographic columns. This is illustrated by separation of several amino acids.