Porogenic Solvent Research Articles

Fluorinated monolithic column for CEC

In order to overcome the drawbacks associated with particle-based fluorinated stationary phases, a fluorinated cationic monolith was successfully synthesized by the in situ copolymerization of a 45% monomer mixture and 55% porogens with thermal initiation using 0.1% initiator with respect to the monomer mixture. The monomer mixture was composed of perfluorododecyl acrylate (49.75%), ethylene dimethacrylate (49.75%), and 0.5% of the quaternary amine acrylic monomer supporting an anodal electroosmotic flow. A tertiary porogenic solvent system consisting of 40% 1-propanol, 40% 1-octanol, and 20% 1-dodecanol was used. The resulting monolith column showed good characteristics in terms of morphology, permeability (pressure drop was 4.8-25.7 MPa between 5 and 25 μL/min), and the electroosmotic mobility (3.68 (±0.05)×10(-4) cm(2) v(-1) s(-1)). The monolith was tested for the separation of four phenolic compounds, three aromatic hydrocarbons, and one fluorine-containing compound. Good efficiencies (up to 135,000 (±4000) plate/m and resolution up to 2.6 (±0.1)) with short analysis time (< 9 min for tau-fluvalinate, <7 min for four phenolic compounds, and <12 min for three aromatic hydrocarbons) and good stability (1.0-1.5% RSD for intraday, 1.2-1.6% RSD for interday, and 3.9-5.0% RSD for column-to-column) were obtained.

Matrine-imprinted monolithic stationary phase for extraction and purification of matrine from Sophorae flavescentis Ait

A matrine-imprinted monolithic stationary phase (MIP monolith) was prepared by in situ polymerization for extraction and purification of matrine from Sophorae flavescentis Ait. Matrine was used as the template molecule, methacrylic acid as the function monomer, ethylene glycol dimethacrylate as the cross-linking agent, and toluene and dodecanol as the porogenic solvents. Scanning electron microscope study revealed that a monolithic structure with mesopores and 36 μm diameter nodules was obtained. The molecular recognition process and the effect of varying chromatographic conditions on separation were examined by high-performance liquid chromatography (HPLC). Hydrogen bonding, electrostatic, hydrophobic interactions and the molecular shape matching in MIP monolith cavities were proposed to be responsible for the recognition mechanism. The use of MIP monolith as a solid-phase extraction (SPE) sorbent for extraction and purification of matrine from S. flavescentis Ait was investigated. The extraction yield was 89.2% (for 3.0 mmol l −1 matrine) with enrichment factor 29.

Effect of porogenic solvent on the morphology, recognition and release properties of carbamazepine‐molecularly imprinted polymer nanospheres

AbstractThis study focus on the effect of the porogenic solvent on the morphology, recognition, and drug release of carbamazepine‐molecularly imprinted polymer nanospheres prepared by precipitation polymerization. The scanning electron microscopy (SEM) images and Brunauer‐Emmett‐Teller (BET) analysis showed that molecularly imprinted polymer (MIP) prepared by acetonitrile exhibited a regular spherical shape at the nanoscale with a high degree of monodispersity, specific surface area of 242 m2 g−1, and pore volume of 1 mL g−1, while those using chloroform and toluene produced irregular polymer particles with low specific surface area and pore volume. MIP prepared by acetonitrile/chloroform (1 : 1, v/v) showed mediator texture properties compared to MIPs obtained by acetonitrile or chloroform. Results from saturation and displacement assays indicated that the imprinted nanospheres with binding capacity of 2.85 (mg CBZ/g polymer) had high specific affinity to CBZ in contrast to nonimprinted nanospheres (1.63 mg CBZ/g polymer). The imprinted nanospheres with 2.4 selectivity factor had good recognition to CBZ than analog template of oxcarbazepine. Moreover, release studies showed that 20% of loaded CBZ was released from the imprinted nanospheres within the initial 6 h, while another 80% of CBZ was released in the following 9 days. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Development of porous polymer monolith by photoinitiated polymerization

Porous polymer monoliths have been successfully prepared by photoinitiated polymerization of butyl methacrylate (BMA) and ethylene glycol dimethacrylate (EDMA) monomers in porogenic solvent of methanol. Mercury intrusion porosimetry and scanning electron microscope are used to characterize the porous properties; nevertheless, the pore size obtained from both techniques is not comparable. The porous structure of the porous polymers is controlled by the phase separation during the polymerization and crosslinking. By varying the composition of the starting solution such as initiator fraction, BMA/EDMA ratio, porogen fraction, and UV intensity, porous polymers with median pore size from about 140 nm to 3 μm can be obtained, and the pore size distribution for majority of the porous polymers is also narrow. The results present a very positive prospect to microfluidic applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Fluorous Monolith Specificity: The Effects of Polymer Density and Secondary Interactions on Column Performance and Amenability to Biological Samples

Continuing from the foundation laid by our previous work in the field, we present here an examination of the effects of monolith density and overall composition on the efficacy of performance in the realm of fluorous separations. By variation of the proportions of monomer and cross-linking agent relative to a static porogenic solvent composition, it was found that a composition of 30% polymer-forming material provides the optimal results in terms of resolution and peak shape for fluorous chromatography of a mixture of similarly labeled benzylamines. The presence of so-called "secondary interactions" that can compete with fluorous specificity in columns of this type were also examined and discussed, with similar results to those observed for commercial fluorous columns being noted. We suggest that these effects may actually be positive if they can be properly harnessed, as the ability to provide a second dimension for fluorous separations based on polarity may allow more complex analyses of labeled proteomic samples to be effectively undertaken. Finally, we present some initial results on the effectiveness of our optimized fluorous monoliths in a series of tagging and separation experiments using a custom-synthesized peptide. With successful resolution of labeled biological samples from their nonfluorous counterparts achieved, we discuss the potential expansion and further applicability of fluorous monoliths of this type in proteomic avenues, as well as their amenability to the greater analytical community.

Preparation and evaluation of monolithic molecularly imprinted stationary phase for S-naproxen

An S-naproxen (S-NAP) molecularly imprinted monolithic stationary phase (MIMSP) with specific recognition for S-NAP and naproxen (NAP) was prepared by in situ technique, utilizing 4-vinylpridine (4-VP) as a function monomer, ethylene glycol dimethacrylate (EDMA) as a cross-linking agent, and low-polar solvents (toluene and dodecanol) as porogenic solvents. The selectivity of the polymers for S-NAP and NAP was evaluated by high performance liquid chromatography (HPLC). The binding characteristics were tested by Scatchard analysis. Racemic NAP could be specifically separated to some extent. At the same time, NAP could be separated from ibuprofen under optimized conditions. Scatchard analysis showed that two classes of binding sites existed in the S-NAP-imprinted polymers, with their dissociation constants estimated to be 1.045 and 5.496μM, respectively. The results demonstrate that S-NAP and NAP can be recognized specifically on the obtained MIMSP.

Preparation of monoliths from single crosslinking monomers for reversed-phase capillary chromatography of small molecules

Highly cross-linked networks resulting from single crosslinking monomers were found to enhance the concentrations of mesopores in, and the surface areas of, polymeric monoliths. Four crosslinking monomers, i.e., bisphenol A dimethacrylate (BADMA), bisphenol A ethoxylate diacrylate (BAEDA, EO/phenol = 2 or 4) and pentaerythritol diacrylate monostearate (PDAM), were used to synthesize monolithic capillary columns for reversed phase liquid chromatography (RPLC) of small molecules. Tetrahydrofuran (THF) and decanol were chosen as good and poor porogenic solvents for BAEDA-2 and BAEDA-4 monoliths. For the formation of the BADMA monolith, THF was replaced with dimethylformamide (DMF) to improve the column reproducibility. Appropriate combinations of THF, isopropyl alcohol and an additional triblock poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) or PPO–PEO–PPO porogen were found to be effective in forming rigid PDAM monoliths with the desired porosities. Selection of porogens for the BADMA and PDAM monoliths was investigated in further detail to provide more insight into porogen selection. Isocratic elution of alkyl benzenes at a flow rate of 0.3 μL/min was conducted for BADMA and PDAM monoliths. The peaks showed little tailing on both monoliths without addition of acid to the mobile phase. The column efficiency measured for pentylbenzene using the BADMA monolithic column was 60,208 plates/m ( k = 7.9). Gradient elution of alkyl benzenes and alkyl parabens was achieved with high resolution. Optimized monoliths synthesized from all four crosslinking monomers showed high permeability, and demonstrated little swelling or shrinking in different polarity solvents. Column preparation was highly reproducible; relative standard deviation (RSD) values were less than 1.2% and 7.5% based on retention times and peak areas, respectively, of alkyl benzenes.

Preparation and evaluation of a phenylboronate affinity monolith for selective capture of glycoproteins by capillary liquid chromatography

A phenylboronate affinity monolith was prepared and applied to the selective capture of glycoproteins from unfractionated protein mixtures. The monolith was synthesized in a 100 μm i.d capillary by an in situ polymerization procedure using a pre-polymerization mixture consisting of 4-vinylphenylboronic acid (VPBA) as functional monomer, ethylene dimethacrylate (EDMA) as crosslinker, diethylene glycol and ethylene glycol as binary porogenic solvents, and azobisisobutyronitrile (AIBN) as initiator. The prepared monolith was characterized in terms of the morphology, pore property, and recognition property. The selectivity and dynamic binding capacity were evaluated by using standard glycoproteins and nonglycoproteins as model proteins. The chromatographic results demonstrated that the phenylboronate affinity monolith had higher selectivity and binding capacity for glycoprotein than nonglycoprotein. The resulting phenylboronate affinity monolith was used as the sorbent for in-tube solid phase microextraction (in-tube SPME), and the extraction performance of the monolith was assessed by capture of ovalbumin from egg white sample.

Preparation of cation-exchange stir bar sorptive extraction based on monolithic material and its application to the analysis of soluble cations in milk by ion chromatography

In this study, a new cation-exchange coating for stir bar sorptive extraction (SBSE) based on poly (acrylic acid-ethylene dimethacrylate) monolithic material was synthesized. The effect of polymerization conditions such as the ratio of functional monomer to cross-linker and the content of porogenic solvent on the extraction efficiencies were investigated in detail. The monolithic material was characterized by elemental analysis, scanning electron microscopy and infrared spectroscopy. In order to evaluate the usability of the new coating for the extraction of inorganic cations, the analysis of soluble K(+), Mg(2+) and Ca(2+) in milk by ion chromatography with conductivity detection was selected as a paradigm. Several extractive parameters, including pH value in sample matrix, desorption solvent, extraction and desorption time were optimized. Under the optimum conditions, low detection limits (S/N = 3) and quantification limits (S/N = 10) of the proposed method for the target cations were achieved within the range of 0.12-0.28 and 0.4-0.92 μg L(-1), respectively. The method also showed good linearity, simplicity, practicality and low cost for the extraction of inorganic cations. Finally, the proposed method was successfully used to analyse three different trademarks of commercial milk samples with satisfactory recoveries in the range of 71.1% to 102.8%.

ROMP-Derived cyclooctene-based monolithic polymeric materials reinforced with inorganic nanoparticles for applications in tissue engineering.

Porous monolithic inorganic/polymeric hybrid materials have been prepared via ring-opening metathesis copolymerization starting from a highly polar monomer, i.e., cis-5-cyclooctene-trans-1,2-diol and a 7-oxanorborn-2-ene-derived cross-linker in the presence of porogenic solvents and two types of inorganic nanoparticles (i.e., CaCO3 and calcium hydroxyapatite, respectively) using the third-generation Grubbs initiator RuCl2(Py)2(IMesH2)(CHPh). The physico-chemical properties of the monolithic materials, such as pore size distribution and microhardness were studied with regard to the nanoparticle type and content. Moreover, the reinforced monoliths were tested for the possible use as scaffold materials in tissue engineering, by carrying out cell cultivation experiments with human adipose tissue-derived stromal cells.

Preparation and Characterization of a Metal-Complexing Imprinted Polymer for Improved Quercetin Recognition

This paper describes the rational design and testing of a new metal-complexing imprinted polymer with enhanced selectivity for Quercetin (Quercetin is a kind of flavonoid which is an important active ingredient of Chinese herbs.). The complex of Quercetin and Cu(II) (Qu-Cu) was used as a template molecule and the mixed solution of methanol and tetrahydrofuran was used as the porogenic solvent. UV–visible spectra was useful to assess the rational ratio of Quercetin to Cu(II). And the evaluation of the various polymers by binding assays revealed that the optimal ratio of the functional monomer to the template was 4:1. The effect of porogenic solvent on molecularly imprinted polymers (MIPs) was studied by transmission electron microscopy (TEM) and equilibrium binding experiments. MIPs were also characterized by Fourier transform infrared spectra (FT-IR). The adsorption behavior for substrates indicated that compared with Quercetin’s structural analogs (Rutin and Naringenin), MIPs exhibited significant adsorption selectivity for Qu in the presence of Cu(II). The separation factors were 5.38 and 7.23, respectively.

Trimethoprim-selective electrodes with molecularly imprinted polymers acting as ionophores and potentiometric transduction on graphite solid-contact

This work proposes a new biomimetic sensor material for trimethoprim. It is prepared by means of radical polymerization, having trimethylolpropane trimethacrylate as cross-linker, benzoyl peroxide as radicalar iniciator, chloroform as porogenic solvent, and methacrylic acid and 2-vinyl pyridine as monomers. Different percentages of sensor in a range between 1 and 6% were studied. Their behavior was compared to that obtained with ion-exchanger quaternary ammonium salt (additive tetrakis(p-chlorophenyl)borate or tetraphenylborate). The effect of an anionic additive in the sensing membrane was also tested.Trimethoprim sensors with 1% of imprinted particles from methacrylic acid monomers showed the best response in terms of slope (59.7mV/decade) and detection limit (4.01×10−7mol/L). These electrodes displayed also a good selectivity towards nickel, manganese aluminium, ammonium, lead, potassium, sodium, iron, chromium, sulfadiazine, alanine, cysteine, tryptophan, valine and glycine. The sensors were not affected by pH changes from 2 to 6. They were successfully applied to the analysis of water from aquaculture.

Synthesis and study of a molecularly imprinted polymer for the specific extraction of indole alkaloids from Catharanthus roseus extracts

Two molecularly imprinted polymers (MIP) for catharanthine and vindoline have been synthesized in order to specifically extract these natural indole alkaloids from Catharanthus roseus by solid-phase extraction (SPE). Each MIP was prepared by thermal polymerisation using catharanthine (or vindoline) as template, methacrylic acid (or itaconic acid) as functional monomer, ethylene glycol dimethacrylate (EDMA) as cross-linking agent and acetonitrile (or acetone) as porogenic solvent. For catharanthine-MIP, a SPE protocol (ACN–AcOH 99/1 washing and MeOH–AcOH 90/10 elution) allows a good MIP/NIP selectivity (imprinting factor 12.6). The specificity of catharanthine-MIP versus related bisindole alkaloids was assessed by cross-reactivity study. The catharanthine-MIP specifically retained catharanthine and its N-oxide analogue but displayed a weak cross-reactivity for other Vinca alkaloids (vinorelbine, vincristine, vinblastine, vindoline, vinflunine). It appears that the catharanthine-like unit of these molecules are hardly trapped in catharanthine cavities located in the MIP, probably due to the sterical hindrance of the vindoline moiety. Finally, the MIP-SPE applied to C. roseus extract enabled quantitative recovery of catharanthine (101%) and the total removal of vindoline. Its capacity was determined and was equal to 2.43 μmol g −1. Vindoline is a weaker base than catharanthine, so the vindoline-MIP was achieved with a strong acidic monomer (itaconic acid) to increase vindoline–monomer interactions and a modified washing solvent (ACN–HCOOH 99/1) to reduce non-specific interactions. The influence of the amount of HCOOH (protic modifier) percolated during the washing step upon the elution yield and the imprinting factor for vindoline was investigated. This preliminary optimisation of the washing step, and in particular the number of moles of acid percolated, seems useful to emphasize the use of MIP in conditions of high selectivity or high yield. A compromise was obtained with an imprinting factor equal to 7.6 and an elution recovery of 33%. However MIP-vindoline failed to achieve a specific extraction of vindoline since catharanthine was also extracted probably because of strong non-specific interactions occurring between catharanthine and the sorbent.

Preparation, evaluation and application of molecularly imprinted solid-phase microextraction monolith for selective extraction of pirimicarb in tomato and pear

A simple, rapid and sensitive method for the determination of pirimicarb in tomato and pear using polymer monolith microextraction (PMME) based on the molecularly imprinted polymer (MIP) monolith combined with high-performance liquid chromatography-photodiodes array detector (HPLC-PAD) was developed. By optimizing the polymerization conditions, such as the nature of porogenic solvent and functional monomer, the molar ratio of the monomer and cross-linker, an pirimicarb MIP monolith was synthesized in a micropipette tip using methacrylic acid (MAA) as the functional monomer, ethylene dimethacrylate (EGDMA) as the cross-linker and the mixture of toluene-dodecanol as the porogenic solvent. The MIP monolith showed highly specific recognition for the template pirimicarb. The monolith was applied for the selective extraction of pirimicarb in tomato and pear. Several parameters affecting MIP-PMME were investigated, including the nature and volume of extraction solvent, sample volume, flow rate and sample pH. Under the optimum PMME and HPLC conditions, the linear ranges were 2.0–1400 μg/kg for pirimicarb in tomato and pear with the correlation coefficient of above 0.999. The detection limits (s/n = 3) were both 0.6 μg/kg. The proposed method was successfully applied for the selective extraction and determination of pirimicarb in tomato and pear.

Synthesis and characterisation of porous polymer microneedles

This paper presents a study on the synthesis of porous polymers with an application to microneedles. A range of Poly (ethylene glycol-co-methacrylic acid) polymers are synthesised using bulk polymerisation techniques to produce porous polymers with various strength and fluid transport characteristics. The synthesised materials are morphologically and mechanically characterised. Using different porogens in the polymer synthesis results in different mechanical strength and fluid flow characteristics. The results indicate that the fluid flow characteristics of the polymers can be sacrificed to improve strength. Optimum polymer strength can be attained by synthesising polymers with macropores that are interconnected via nanopores using the minimum amount of porogenic solvents.

Naphthyl methacrylate‐phenylene diacrylate‐based monolithic column for reversed‐phase capillary electrochromatography via hydrophobic and π interactions

A neutral naphthyl methacrylate-phenylene diacrylate-based monolith (NPM) was introduced for RP-CEC of various neutral and charged solute probes via hydrophobic and π interactions. The NPM column was prepared by the in situ polymerization of naphthyl methacrylate as the functional monomer and 1,4-phenylene diacrylate (PDA) as the crosslinker in a ternary porogenic solvent containing cyclohexanol, dodecanol and water. The NPM column exhibited cathodal EOF despite the fact that it was devoid of any fixed charges. NPM exhibited stronger EOF than its counterpart naphthyl methacrylate monolith (NMM) made from the in situ polymerization of naphthyl methacrylate and trimethylolpropane trimethacrylate (TRIM). As for NMM, it is believed that the EOF arises from the adsorption of mobile phase ions onto the monolith surface. The higher EOF exhibited by NPM may be attributed to the acrylate nature of PDA as compared to the methacrylate nature of TRIM, and therefore PDA has a higher binding capacity for mobile phase ions due to its higher polarity than TRIM. The adsorption of mobile phase ions together with the additional π interactions offered by the aromatic rings of the NPM matrix modulated solute retention and separation selectivity. The applications of NPM were demonstrated by the separation of a wide range of small and large solutes including peptides, tryptic peptide maps and proteins.

A novel, neutral hydroxylated octadecyl acrylate monolith with fast electroosmotic flow velocity and its application to the separation of various solutes including peptides and proteins in the absence of electrostatic interactions

A neutral hydroxylated octadecyl monolith (ODM-OH) for reversed-phase capillary electrochromatography has been developed. The ODM-OH was prepared by the in situ polymerization of octadecyl acrylate and pentaerythritol triacrylate (PETA) in a ternary porogenic solvent. Pentaerythritol triacrylate possesses a hydroxyl functional group, which imparts the monolith with a hydrophilic group, thus the acronym ODM-OH. The ODM-OH column exhibited cathodal EOF over a wide range of pH and ACN concentration in the mobile phase despite the fact that it was devoid of any fixed charges. This ODM-OH monolith exhibited stronger EOF than its counterpart the ODM made from the in situ polymerization of octadecyl acrylate and trimethylolpropane trimethacrylate. Similar to ODM, it is believed that the EOF was due to the adsorption of ions from the mobile phase onto the surface of the monolith thus imparting the neutral monolithic column the zeta potential necessary to support the EOF. The higher EOF exhibited by ODM-OH was due to the presence of polar OH groups on its surface, which would favor stronger adsorption of ions from the mobile phase. The wide applications of the neutral ODM-OH column were demonstrated in the separation of a wide range of small and large solutes. As a typical result, the ODM-OH was able to separate proteins quite rapidly yielding 200,000 plates/m.

A Study of Polymerization‐Induced Phase Separation as a Route to Produce Porous Polymer–Metal Materials

We report the results of the experimental study of the preparation of hybrid porous polymer material carrying gold nanorods (NRs) on the surface of pores. The material was prepared by utilizing two effects occurring concurrently: the photoinitiated polymerization-induced phase separation in the polymer-solvent mixture and the migration of the NRs to the interface between the polymer and the porogen solvent. We show that the enrichment of the interface with the NRs is enhanced at high polymerization rate leading to the rapid phase separation. By contrast, more rapid increase in viscosity achieved at high polymerization rate does not have a significant effect on the segregation of NRs to the surface of pores.

Ring‐Opening Metathesis Polymerization‐Based Synthesis of CaCO3 Nanoparticle‐Reinforced Polymeric Monoliths for Tissue Engineering

Porous monolithic materials have been prepared via ring-opening metathesis polymerization from norborn-2-ene and a 7-oxanorborn-2-ene-based cross-linker in the presence of porogenic solvents (i.e., 2-propanol and toluene) and norborn-2-enephosphonate surface-modified CaCO(3) nanoparticles, using the 3(rd) -generation Grubbs-initiator RuCl(2) (Py)(2) (IMesH(2) )(CHPh). The experimental setup and the conditions chosen allowed for the manufacturing of polymeric monoliths characterized by a homogeneous distribution of the inorganic nanoparticles throughout the polymeric monolith. Depending on the nanoparticle content, the macropore diameters could be varied in the 30-120 µm regime. Noteworthy, the addition of nanoparticles did not affect the phase separation-triggered formation of the monolithic matrix nor the meso- and microporosity as evidenced by N(2) -adsorption experiments.

Preparation and characterization of a molecularly imprinted monolithic column for pressure‐assisted CEC separation of nitroimidazole drugs

A polymethacrylate-based molecularly imprinted monolithic column bearing mixed functional monomers, using non-covalent imprinting approach, was designed for the rapid separation of nitroimidazole compounds. The new monolithic column has been prepared via simple in situ polymerization of 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate and ethylene dimethacrylate, using (S)-ornidazole ((S)-ONZ) as template in a binary porogenic mixture consisting of toluene and dodecanol. The composition of the polymerization mixture was systematically altered and optimized by altering the amount of monomers as well as the composition of the porogenic solvent. The column performance was evaluated in pressure-assisted CEC mode. Separation conditions such as pH, voltage, amount of organic modifier and salt concentration were studied. The optimized monolithic column resulted in excellent separation of a group of structurally related nitroimidazole drugs within 10 min in isocratic elution condition. Column efficiencies of 99 000, 80 000, 103 000, 60 000 and 99 000 plates/m were obtained for metronidazole, secnidazole, ronidazole, tinidazole and dimetridazole, respectively. Parallel experiments were carried out using molecularly imprinted and non-imprinted capillary columns. The separation might be the result of combined effects including hydrophobic, hydrogen bonding and the imprinting cavities on the (S)-ONZ-imprinted monolithic column.