A benzenesulfonic acid-modified organic polymer monolithic column with reversed-phase/hydrophilic bifunctional selectivity for capillary electrochromatography

Here,a styrene-based polymer monolithic column poly(VBS-co-TAT-co-AHM)with reversed-phase/hydrophilic interaction liquid chromatography(RPLC/HILIC)bifunctional separation mode was success-fully prepared for capillary electrochromatography by the in situ polymerization of sodium p-styrene sulfonate(VBS)with cross-linkers 3-(acryloyloxy)-2-hydroxypropyl methacrylate(AHM)and 1,3,5-triacryloylhexahydro-1,3,5-triazine(TAT).The preparation conditions of the monolith were optimized.The morphology and formation of the poly(VBS-co-TAT-co-AHM)monolith were confirmed by scanning electron microscopy(SEM)and Fourier transform infrared spectroscopy(FT-IR).The separation perfor-mances of the monolith were evaluated systematically.It should be noted that the incorporation of VBS functional monomer can provideπ-πinteractions,hydrophilic interactions,and ion-exchange in-teractions.Hence,the prepared poly(VBS-co-TAT-co-AHM)monolith can achieve efficient separation of thiourea compounds,benzene series,phenol compounds,aniline compounds and sulfonamides in RPLC or HILIC separation mode.The largest theoretical plate number for N,N0-dimethylthiourea reached 1.7×10^(5)plates/m.In addition,the poly(VBS-co-TAT-co-AHM)monolithic column showed excellent reproducibility and stability.This novel monolithic column has great application value and potential in capillary electrochromatography(CEC).

Chiral separation by (S)-naproxen imprinted monolithic column with mixed functional monomers

Molecularly imprinted polymers （MIPs）, using （S）-naproxen as template and the combination of butyl methacrylate （BMA） and MAA （1：1 molar ratio） as functional monomers were synthesized by an in situ polymerization reaction. The rendered monolithic column was evaluated in HPLC mode. The result showed that the monolithic MIPs with the combination of two monomers produced better chiral resolution of rac-naproxen （Rs = 1.55） and column efficiencies of imprinted molecules （N = 2860 plates/m） than that with pure MAA.

Evaluation of the clenbuterol imprinted monolithic column prepared by reversible addition-fragmentation chain transfer polymerization

To make more homogenous organic monolithic structure, reversible addition-fragmentation chain transfer （RAFT） process was employed in the synthesis of the clenbuterol imprinted polymer. In the synthesis, the influence of synthetic conditions on the polymer structure and separation efficiency was studied. The result demonstrated that the imprinted columns prepared with RAFT process have higher column efficiency and selectivity than the columns prepared with conventional polymerization in the present study, which may result from the higher surface area, smaller pore size and the narrower globule size distribution in their structures. The result indicated that RAFT polymerization provided better conditions for the clenbuterol imprinted monolithic polymer preparation. 2009 Xiang Chao Dong. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Rapid Preparation of Monolithic Columns for Capillary Electrochromatography Separation

Fritless packed silica gel columns were prepared using sol-gel technology, The part of a 75 μm i.d. capillary was filled with a mixture of methacryloxypropyltrimethoxysilane, toluene and hydrochloric acid. Four different photoinitiators such as benzoin methyl ether, Irgacure 819, Irgacure 1700 and Irgacure 1800 were added in the presence or absence of sodium dodecyl sulfate during the polymerization process. The above eight solutions were irradiated at 365 nm about 5-10 min to prepare the porous monolithic sol-gel columns by a one-step process.

Novel preparation of organic polymer-based monolithic column by microwave irradiation

Microwave irradiation was firstly attempted for the preparation of organic-based monoliths of poly（styrene-divinylbenzene- methacrylic acid）, which single step in situ polymerization was carried out during 15 min. The colunm permeability, electrophoretic and chromatographac behaviors were comparatively evaluated using pressure-assisted CEC, GEC and low pressure-driven separation modes. The largest theoretical plates for the preparing column could be close to 18,0000 plates/m for thiourea in the mode of p-CEC. It provided a viable alternative to traditional initiation means for the perparation of monolithic capillary columns.

Determination of L-norvaline and L-tryptophan in dietary supplements by nano-LC using an O-[2-(methacryloyloxy)-ethylcarbamoyl]-10,11- dihydroquinidine-silica hybrid monolithic column

An analytical methodology based on an O-[2-(methacryloyloxy)-ethylcarbamoyl]-10,11-dihydroquinidine(MQD)-silica hybrid monolithic column was developed for the enantioseparation of 9-fluorenylmethoxycarbonyl(FMOC)derivatized amino acids by nano-liquid chromatography.The mobile phase was optimized including the apparent pH,content of ACN,and concentration of the buffer to obtain a satisfactory enantioresolution performance.27 FMOC derivatized amino acids including 19 protein and 8 non-protein amino acids were tested,and 19 out of them were enantiomerically discriminated obtaining baseline separation for 11 of them.Analytical characteristics of the method were evaluated for norvaline and tryptophan in terms of linearity,precision,accuracy,limits of detection(LOD)and quantitation(LOQ)showing good performance to be applied to the enantiomeric determination of these amino acids in dietary supplements.LOD and LOQ values were 9.3 and 31 mM for norvaline enantiomers and 7.5 and 25 mM for tryptophan enantiomers,respectively.The contents of D-norvaline and D-tryptophan were below their respective LODs in all the analyzed samples.Quantitation of L-tryptophan and L-norvaline showed good agreement with the labeled contents except for one sample which did not show presence of L-norvaline,contrary to the label indication.

Preparation of Polymeric Monolithic Column and Application to the Resolution of Aromatic Compounds in Capillary Electrochromatography

Polymeric monolithic capillary column-poly(GMA-co-EDMA-co-AMPS) was prepared andused for resolution of aromatic compounds (benzalcohol, 2-phenylethanol, toluene, ethylbenzene).

Novel Method of Preparation of Monolithic Columns for Fast Separation byγ-Ray Irradiation

A porous monolithic sol-gel column with the solution of methacryloxypropyltrimethoxysilane in toluene with an acid catalyst was prepared in the presence and absence of sodium dodecyl sulfate. In situ polymerization was carded out by γ-ray irradiation within the capillary. The γ-radiation-initiated synthesis could generate radicals directly on the monomer avoiding use of any initiator. The chromatographic behavior of the capillary monolithic columns were studied in the modes of CEC, p-CEC and low pressure-driven separation, all the tests exhibited reversed-phase character. It provided a viable alternative to either thermally initiated or photo polymerization method for the preparation of monolithic columns.

Preparation of Monolithic Column and Its Application in p-CEC

A novel monolithic stationary phase having long alkyl chain ligands was introduced and evaluated in pressurized-capillary electrochromatography of small neutral and charged compounds. The monolithic column was prepared by the in situ copolymerization of ethylene dimethacrylate, 1-hexadecene, allyl alcohol and 2-acrylamido-2-methyl-1-propanesulfonic acid in a quaternary porogenic solvent mixture consisting of 1, 4-butanediol, cyclohexanol, dodecanol and water.

Fast preparation of photopolymerized monolithic columns for capillary electrochromatography

Photopolymerized sol-gel(PSG) columns were prepared using methacryloxypropyltrimethoxysilane as the monomer,toluene as the porogen and hydrochloric acid as the catalyst.Four different photoinitiators such as benzoin methyl ether,Irgacure 819,Irgacure 1700 and Irgacure 1800 were comparatively used in the reaction solution in the presence and absence of sodium dodecyl sulfate.The above eight solutions were respectively irradiated at 365 nm for 5?10 min in each capillary(75 μm inside diameter) to prepare the porous monolithic sol-gel column by a one-step,in situ,process.The chromatographic behavior of the eight PSG columns were comparatively studied,all of which exhibit reversed-phase character.Using these columns,several neutral compounds,namely thiourea,benzene,toluene,ethyl benzene,biphenyl and naphthalene can be separated from mixtures with a largest column efficiency of 74 470 plate/column for thiourea.Addition of sodium dodecyl sulfate in the polymerization process has a significant influence on the morphology and migration time.

Rapid and simultaneous determination of imidazolium and pyridinium ionic liquid cations by ion-pair chromatography using a monolithic column

A method for rapid and simultaneous determination of imidazolium and pyridinium ionic liquid cations by ion-pair chromatography with ultraviolet detection was developed. Chromatographic separations were performed on a reversed-phase silica-based monolithic column using 1-heptanesulfonic acid sodium-acetonitrile as mobile phase. The effects of ion-pair reagent and acetonitrile concentration on retention of the cations were investigated. The retention times of the cations accord with carbon number rule. The method has been successfully applied to the determination of four ionic liquids synthesized by organic chemistry laboratory.

Preparation of imprinted monolithic column under molecular crowding conditions

Molecular crowding is a new concept to obtain molecularly imprinted polymers（MIPs） with greater capacity and selectivity.In this work,molecular crowding agent was firstly applied to the preparation of MIPs monolithic column.A new polymerization system based on molecular crowding surrounding was developed to prepare enrofloxacin-imprinted monolith,which was composed of polystyrene and tetrahydrofuran.The result showed that the monolithic MIPs under molecular crowding conditions presented good molecular recognition for enrofloxacin with an imprinting factor of 3.03.

Novel preparation of monolithic imprinted columns for electrochromatographic separation by photopolymerization

A monolithic molecularly imprinted polymer with specific recognition ability for 4-hydroxybenzoic acid (4-HBA) was prepared by in situ photopolymerization, using methacrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EDMA) as a cross-linking agent, toluene and isooctane as porogenic solvents and Irgacure 1800 as an initiator. Baseline separation of isomers of hydroxybenzoic acid was achieved in less than 8 min on this monolithic column using 4-HBA as template, but not on the blank polymer. Furthermore, some neutral compounds could also be baseline-separated on the imprinted polymer column in the mode of pressure-driven capillary electrochromatography.

Molecularly Imprinted Polymer Monolithic Column Separation of Isomers and Analogues of Vanillin by Capillary Electrochromatography

A vanillin imprinted capillary monolithic column was synthesized by in situ polymerization reaction using ethylene-glycol dimethacrylate as cross-linking monomer and methacrylic acid as functional monomer. Under the optimum conditions of capillary electrochromatography, this molecularly imprinted polymer （MIP）-based column showed high selectivity and could recognize not only template molecule vanillin but also positional isomer o-vanillin from their structural analogues.

A hybrid monolithic column based on flower-shaped zeolitic imidazolate framework for efficient capillary microextraction of brominated flame retardants

A novel flower-shaped zeolitic imidazolate framework(ZIF) doped organic-inorganic hybrid monolithic column(ZIF-HMC) was prepared by a simple sol-gel "one-step" method and utilized for efficient capillary microextraction(CME) of four brominated flame retardants.The prepared monolithic was characterized by Fourier transform infrared,scanning electron microscopy,X-ray photoelectron spectroscopy,energy disperse spectroscopy,and N_(2) adsorption-desorption.The parameters of CME were optimized by orthogonal array design.Under the optimal conditions,the ZIF-HMC showed excellent extraction efficiency,the limit of detection(LODs) and the limit of quantification(LOQs) were in the range of0.52$3.1 mg/L and 1.7$10 mg/L,respectively,and the proposed method demonstrated good recovery(88.8%–116.6%) with the RSD less than 13.6% and a reusability of at least 30 times.The ZIF-HMC possessed great potential for separating organic pollutants and the strategy used here could be extended to prepare other derivatized HMC functionalized monoliths.

Ionic Liquid 1-Vinyl-3-dodecylimidazole Bromide Embedded Hybrid Monolithic Column and Its Versatile Post-modification with Amino Acids

The amino acids post-modified ionic liquids-based hybrid monolithic columns were successfully developed.For the first step,using 1-vinyl-3-dodecylimidazole bromide(VDI·Br)and polyhedral oligomeric silsesquioxane methacryl substituted(POSS-MA)as monomer and crosslinking agent,the monolithic POSS-VDI matrix material was polymerized in 100μm capillary.The prepared POSS-VDI column is of ion-exchange/reverse-phase mixed-mode retention characteristics.The column e fficiency reached 137,000 N/m for thioureas.The POSS-VDI column has also been successfully applied to recognize and analyze the eff ective components of Traditional Chinese Medicines Fangji and the Root of Kudzu Vine.Furthermore,based on its good chromatographic performances,in the second step,amino acids L-Proline(L-Pro),Glycine(Gly)or DLPhenylalanine(DL-Phe)were further exploited as the anion exchangers to post-modify the POSS-VDI column.The new POSS-VDI-Pro,POSS-VDI-Gly and POSS-VDI-Phe columns exhibited diff erent separation selectivity for the complex egg white protein sample.The present work provides a good route to fabricate versatile amino acids and ionic liquids modified monolithic columns with good separation selectivity.

Determination of phthalate esters in physiological saline solution by monolithic silica spin column extraction method

Monolithic silica spin column extraction （MonoSpin-SPE） was developed as a simple, sensitive, and eco-friendly pretreatment method which combined with ultra-fast liquid chromatography-mass spectrometry （UFLC-MS） to determine the levels of six phthalate esters, dimethyl- （DMP）, diethyl- （DEP）, dipropyl- [ DPrP], butyl-benzyl- （BBP）, dicyclohexyl- （DcHP）, and di-n-octyl-（DOP） phthalate in physiological saline samples. Under optimized experimental conditions, the method was linear in the following ranges： 0.2- 50 μg/L for DMP, DEP, DPrP, DcHP and DOP; 5- 100 μg/L for BBP. The correlation coefficients （R2 ） were in the range of 0. 9951 - 0. 9995 for all the analytes and the limits of detection （LODs） and limits of quantification （LOQs） were in the ranges of 0.02 - 0.9 μg/L and 0.08 - 2.7μg/L, respectively. The pretreatment process showed good reproducibility with inter-day and intra-day relative standard deviations （RSDs） below 8.5% and 11.2%, respectively. This method was used to determine the levels of six phthalate esters in physiological saline samples and the recoveries ranged from 71.2% to 107.3%. DMP and DEP were found in actual physical saline samples （brand A and brand B）.

An enrichment device of silica-based monolithic material and its application to determine micro-carbaryl by NIRS

Silica-based monolithic column material was synthesized and an enrichment device was fabricated with the material by assembling the material inside a glass column. The enrichment device was applied for the determination of micro-carbaryl with near-infrared spectroscopy （NIRS）. The aqueous solutions of carbaryl passed through the device and the carbaryl was enriched on the surface of the material where diffuse reflection NIR spectra were measured. These procedures of enrichment and measurement ensured to concentrate analytes for the measurement, so that the sensitivity of determination of MRS could be improved. NIR spectra of carbaryl solutions （0.01-1.00μg mL^-1）, measured after the application of the enrichment device, were pretreated with multiplicative scatter correction （MSC） and regressed against the concentrations of the carbaryl solutions with partial least squares （PLS） method. The results showed that the minimum value of root-mean-square error of prediction （RMSEP） was 0.1771 μg mL^-1 when the number of latent variables was 3 of PLS regression. Therefore, the number of latent variables 3 was selected as the optimum value. RMSEP was not very low but acceptable considering that NIRS is commonly used in macro amount analysis and it is quite difficult for NIRS to determine micro amount analytes, especially, less than 1 μg mL^-1.

Seismic behavior of precast segmental column bridges under near-fault forward-directivity ground motions

Precast segmental column bridges exhibit various construction advantages in comparison to traditional monolithic column bridges.However,the lack of cognitions on seismic behaviors has seriously restricted their applications and developments.In this paper,comprehensive investigations are conducted to analyze the dynamic characteristics of precast segmental column bridges under near-fault,forward-directivity ground motions.First,the finite-element models of two comparable bridges with precast segmental columns and monolithic columns are constructed by using OpenSees software,and the nonlinearities of the bridges are considered.Next,three different earthquake loadings are meticulously set up to handle engineering problems,namely recorded near-and far-field ground motions,parameterized pulses,and pulse and residual components extracted from real records.Finally,based on the models and earthquake sets,extensive explorations are carried out.The results show that near-fault forward-directivity ground motions are more threatening than far-field ones;precast segmental column bridges may suffer more pounding impacts than monolithic bridges;the“narrow band”effect caused by near-fault,forward-directivity ground motions may occur in bridges with shorter periods than pulse periods;and pulse and residual components play different roles in seismic responses.

Determination of bisphosphonates anti-resorptive properties based on three forms of ceramic materials: Sorption and release process evaluation

There is a strong need to search for more effective compounds with bone anti-resorptive properties,which will cause fewer complications than commonly used bisphosphonates. To achieve this goal, it is necessary to search for new techniques to characterize the interactions between bone and drug. By studying their interaction with hydroxyapatite(HA), this study used three forms of ceramic materials,two of which are bone-stimulating materials, to assess the suitability of new active substances with antiresorptive properties. In this study, three methods based on HA in loose form, polycaprolactone/HA(a polymer-ceramic materials containing HA), and polymer-ceramic monolithic in-needle extraction(MINE) device(a polymer inert skeleton), respectively, were used. The affinity of risedronate(a standard compound) and sixteen aminomethylenebisphosphonates(new compounds with potential antiresorptive properties) to HA was defined according to the above-mentioned methods. Ten monolithic materials based on 2-hydroxyethyl methacrylate/ethylene dimethacrylate are prepared and studied, of which one was selected for more-detailed further research. Simulated body fluids containing bisphosphonates were passed through the MINE device. In this way, sorptionedesorption of bisphosphonates was evaluated using this MINE device. The paper presents the advantages and disadvantages of each technique and its suitability for assessing new active substances. All three methods allow for the selection of several compounds with potentially higher anti-resorptive properties than risedronate, in hope that it reflects their higher bone affinity and release ability.