Search

Okadaic acid (OA) biotoxin acts a well-established inhibitor of protein phosphatase even a tumor promoter of human being, arouse great attention in safety monitoring. However, the powerful and convenient nanosensing technologies for addressing the demands such as rapidity, high sensitivity, and stability in the in-field test of OA shellfish toxin is still scarce. Herein, a high-performance magnetic biometric nanosensor (MBNS) integrating oriented aptamers and ultrasensitive laser-induced fluorescence (LIF) was firstly proposed for the in-field detection of trace OA in seafoods. High-density aptamers hybridized with FAM-labeled cDNA were tethered to the surface of AuNPs on magnetic MIL-101@Fe 3 O 4 , and then finely regulated by mercaptohexyl alcohol (MCH) to be orderly assembled, as was successfully utilized to engineer an active biological nanosensor for highly specific recognition of OA. Aptamers anchored on magnetic Fe 3 O 4 @MOF@AuNPs activate a biometric microreactor of OA, in which the superior LIF properties, conformation regulation of aptamer, and the specific recognition using aptamer genes were adopted. The magnetic nanosensor with an excellent specificity and super sensitivity for OA analysis was achieved within 20 min. Moreover, the content of captured OA could facilely be recorded by measuring the fluorescence intensity, and the limit of detection (LOD) and limit of quantitation of OA (LOQ) reached 0.015 and 0.050 ng/mL respectively, which was far better than most aptamer-based biometric sensing methods. The feasibility for accurate test of trace OA toxin in the fortified shellfish samples was validated with the recovery yields of 88.2-107.5% and RSD of 0.5-7.6%, respectively. The result demonstrated that the oriented-aptamer encoded MNS had significant practical values in rapid and ultrasensitive detection of OA biotoxin and the related safety applications., Competing Interests: Declaration of Competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Developing functional fiber coating for selective solid phase microextraction (SPME) of trace pollutants is critical in environmental analysis. Herein, the novel covalent organic frameworks (COFs) with three-dimensional (3D) frameworks and multiple interactions were designed and presented for the selective SPME of polychlorinated biphenyls (PCBs). Using tetra (p-aminophenyl) methane (TAM) and 1,3,5-triformylphloroglucinol (Tp) as the monomers, the 3D TpTAM-COF was synthesized and possessed a large specific surface area, high thermal stability, and spatial selectivity toward PCBs. Characterizations such as morphology, XPS, XRD, thermal stability, and enhancement factors (EFs) were studied. Multiple interactions including π-π conjugation, hydrophobic interaction, and selectivity toward non-planar structure were adopted, which resulted in a superior adsorption affinity toward PCBs on TpTAM-COF. Under the optimal conditions, the spatial selectivity toward PCBs, organic analogs (o-dichlorobenzene, biphenyl) and polycyclic aromatic hydrocarbons (naphthalene, pyrene, and anthracene)) was achieved. Efficient and selective adsorption of fifteen PCBs was fulfilled with the highest EF up to 10305. Using the HS-SPME-GC-MS method, the recoveries of PCBs in the river water and soil samples were determined to be 84.8 ± 7.8% ∼ 117.2 ± 8.5% (n = 3) and 84.4 ± 8.6% ∼ 114.7 ± 7.6% (n = 3), respectively. Compared with most commercial SPME fibers and other COFs-based fibers, the resultant TpTAM-COF-coated fibers possessed higher selectivity and EFs of PCBs. It proposed a promising approach for selective SPME of trace PCBs by multiple interactions in the steric structure of 3D COFs., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest. We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled “Efficient and selective solid-phase microextraction of polychlorinated biphenyls by using a three-dimensional covalent organic framework as functional coating”., (Copyright © 2022 Elsevier B.V. All rights reserved.)

A novel hybrid material (ZIF-7-NH 2 @MIP) combining high adsorption capacity of amino-functional zeolitic imidazolate framework and specific recognition ability of dual-template molecular imprinted polymer was synthesized. The prepared ZIF-7-NH 2 @MIP was characterized by a range of instrumental techniques and combined with high performance liquid chromatography for the detection of four phthalate esters. The limits of detection of the four PAEs were below the maximum residue limit of GB 3838-2002 in China, ranging from 0.04 to 0.08 μg L -1 . The recoveries of the three real samples of mineral water, carbonated drinks and pulpy juices spiked at 10 μg L -1 were 88.68-98.58% and the relative standard deviations was 1.19-3.40%. The above results showed that the obtained absorbent exhibited many advantages for extracting analytes in aqueous solution especially complex environment due to the combination of the superior hydrothermal and large specific surface area of the amino-functionalized ZIF-7-NH 2 and the specific identification of the dual-template molecular imprinted polymer., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

A novel aptamer-functionalized metal-organic framework nanofibrous composite (viz. PAN/UiO@UiO2-N 3 -aptamer) with a high aptamer coverage density was proposed based on the electrospinning and seeded growth method, and used for specific affinity recognition of trace Microcystin-LR (MC-LR). Heterobifunctional ligand was used to modify the metal-organic framework nanoparticles (MOF NPs) surface, which could passivate the MOF surface with respect to unmodified DNA, followed by coupling massive aptamers on MOF of the solid-phase microextraction (SPME) fiber using click chemistry. Characterizations including morphology, spectra analysis, mechanical stability, binding capacity and specificity were fulfilled. Applied to the analysis of MC-LR, the good selective and sensitive recognition were obtained with the detection limit as low as 0.003 ng/mL, which was better than most non-specific SPME or solid-phase extraction (SPE) protocols. The stability and reproducibility were acceptable, and the intra-day, inter-day and column-to-column relative standard deviations (RSDs) for the recovery of MC-LR were gained in the range from 2.5% to 14.3%, respectively. Satisfactory recoveries of MC-LR in environmental water samples were measured as 96.3 ± 4.7% - 98.9 ± 2.7% (n = 3) in tap water, 94.4 ± 2.5% - 96.1 ± 3.5% (n = 3) in pond water, and 97.0 ± 2.1% - 97.9 ± 3.1% (n = 3) in river water, respectively. This work demonstrated that the electrospun nanofibrous composite with massive aptamers would be a better alternative for ultra-trace MC-LR detection with good selectivity, matrix-resistance ability and high resolution., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Herein, a facile protocol of simple DNA adsorption on UV-initiated polymerization supports was proposed for effectively fabricating aptamer-based affinity monolithic column. Hydrophilic cationic monolith with an excellent mechanical stability was achieved within 7 min and then massive aptamers were directly bound by DNA charge-dependent adsorption. Strong cationic quaternary ammonium-based monomer was employed to provide effective and stable positive charge surface for aptamer immobilization in a wide range of pH. An ultra-high aptamer coverage density of 6813 pmol/μL was achieved to gain a highly specific online recognition performance. Limitations such as low aptamer capacity, tedious modification and time-consuming reactions in the traditional biological or covalent modification strategies were avoided. By using ochratoxin A (OTA) as the given analyte, the selective recognition and high recoveries were successfully achieved, and little cross-reactivity towards OTB analogue was only 0.5% even if the content of OTB got up to 125 folds of OTA. Applied to sample analysis, the satisfactory discriminations of trace OTA were obtained at 93.9 ± 1.9% - 96.5 ± 1.7%（n = 3）in beer, wheat and chicken liver samples. It might light a cost-effective access to efficiently preparing high-performance affinity monoliths towards the selective in-tube microextraction of OTA., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

A novel aptamer@AuNPs@UiO-66-NH 2 electrospun nanofibrous coating fiber for specific recognition of microcystin-LR (MC-LR) was proposed by using electrospinning, metal-organic frameworks (MOF) seed growth and AuNPs bridging aptamer strategies. Characterization of morphology, structure and stability of the obtained affinity nanofibrous coating fiber were investigated. High loading of MOFs and aptamers on the nanofibrous fiber were achieved and successfully applied for accurate identification of MC-LR by solid-phase microextraction (SPME) coupled with LC-MS. Highly specific recognition of MC-LR with little interference of analogs was achieved with extremely low LOD (0.004 ng/mL), good precision (CV% < 11.0%) and low relative error (RE% = -1.5% to -10.0%), which was rather better than that of the traditional SPME or SPE protocols. Satisfactory recoveries of MC-LR were obtained in the range of 92.0-96.8% (n = 3) in fortified tap water, raw pond water and river water samples. This work revealed an attractive alternative access to specific recognition and super-sensitive analysis of MC-LR in water., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

Chiral compounds are known to be important not only because they are the fundamental components of living organisms, but also for their unique chiroptical properties. In recent years, scientists have fabricated several chiral organic supramolecular aggregates by using chiral physical fields, such as vortex flow. Herein, the relationship between dynamic chiroptical properties and rheological nature is discussed, suggesting the shear thinning properties of non-Newtonian fluids might help colloidal particles adopt a chiral arrangement in vortices. Furthermore, the storage modulus of colloids could be increased by adding a linking agent, which successfully kept the dynamic chiroptical properties in the static state. Moreover, the salt effect on the host-guest interaction involved in the colloids was studied, the results suggested a significant enhancement of the transferred dynamic circular dichroism for the achiral guest molecule., (© 2021 Wiley-VCH GmbH.)

A photo-initiated polymerized oligonucleotide-grafted hydrophilic affinity monolithic column was synthesized in situ, and exploited for selective in-tube solid phase micro-extraction (IT-SPME) protocol towards the sensitive detection of ochratoxin A (OTA). Only 7 min was required for the rapid polymerization of aptamer-based affinity monolith, which was much less than the reaction time of most thermal polymerization (12-16 h) and sol-gel chemistry methods (up to 52 h). Characterizations such as polymerization recipes, structure morphology, FTIR spectrum, elemental mapping, mechanical stability, and specific recognition performance were evaluated. A significantly hydrophilic nature with a low contact angle of 15° was observed, and a mixed-mode mechanism including aptamer affinity recognition and hydrophilic interaction (HI) was employed. By coupling with HPLC-fluorescence detection, the highly specific online recognition performance was achieved with an extremely low nonspecific adsorption of the analogues. The calibration curve of OTA was obtained in the concentration range 0.05-50.00 ng·mL -1 with a limit of detection (LOD, S/N = 3) of 0.012 ng·mL -1 . Applied to sample analysis, acceptable recovery yields of 95.1 ± 1.4% - 99.5 ± 2.2% (n = 3) were obtained in beer and red wine. The proposed method lighted a promising way to efficiently preparing a hydrophilic aptamer-affinity monolith for highly specific recognition of trace mycotoxin by IT-SPME coupled with HPLC. A hydrophilic oligonucleotide-based affinity capillary monolith was explored via in situ photopolymerization for overcoming low preparation efficiency and achieving high-performance online IT-SPME of OTA mycotoxin., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Developing a functional affinity monolithic column towards in-tube solid-phase microextraction (IT-SPME) for selective sample pretreatment is critical. Herein, a high-performance capillary affinity monolithic column with an ultra-high aptamer coverage density was rapidly fabricated via a simple adsorption strategy, in which aptamers with natural sequences were directly immobilized on an ammonium-based strongly cationic matrix. Limitations of the traditional biological or covalent methods such as time-consuming modification reactions, special requirement of active groups ( e.g. -NH 2 and -SH) on the aptamer, and low aptamer coverage density levels were avoided. An ultra-high coverage density of 8616 pmol μL -1 was achieved with excellent stability, and the highest aptamer-modification level among all the current methods was reached. Selective recognition and high recovery yields of the model mycotoxin ochratoxin A (OTA) were achieved in 95.9 ± 0.98%-97.9 ± 0.28% ( n = 3). In particular, there was little cross-reactivity towards the OTB analogue of only 0.5% even in the case of 250 fold of the analogue OTB, which was not reported in previous affinity monoliths. Upon sample analysis, satisfactory discriminations of trace OTA were obtained at 93.7 ± 1.4%-95.5 ± 2.5% ( n = 3) in beer and wheat. A facile and direct method for efficiently fabricating an aptamer-based affinity monolith towards online selective IT-SPME was proposed.

Covalent organic frameworks (COFs) showed great promise in effective adsorption of target molecule via size selectivity. Although various magnetic 2D COFs composites have been studied and exhibited the intensive applications, the incorporation of 3D COFs and magnetic nanoparticles to form a new class of magnetic adsorbents with enhanced function still has no reports. Herein, a novel Fe 3 O 4 @3D COF with heteroporous structure matching to the sizes of bisphenol A (BPA) was firstly synthesized for better adsorption of BPA than common magnetic 2D-COFs. Three Fe 3 O 4 @3D COFs nanospheres were synthesized under the solvothermal conditions in autoclave, and the optimum Fe 3 O 4 @3D-COF denoted as Fe 3 O 4 @COF-TpTAM (Tp, 1,3,5-triformylphloroglucinol; TAM, tetra(p-aminophenyl)-methane) was selected and employed. Detailed characteristics of Fe 3 O 4 @COF-TpTAM were evaluated via various techniques including TEM, FTIR, TGA, XRD and BET. Excellent chemical and thermal stability, high surface area (294.6 m 2  g -1 ) and pore volume (0.2 m 3  g -1 ) with multiple pore sizes comparable with the simulated three-dimensional sizes of BPA were exhibited. A high adsorption capacity of BPA up to 209.9 mg/g that was better than common 2D-COFs was achieved, and the sensitive MSPE-LC-MS method with wide linear range (10-5000 pg/mL), low detection limit (4 pg/mL, S/N = 3) was built. Satisfactory recoveries of BPA as 93.8 ± 1.4%-101.4 ± 5.1% (n = 3) and 100.4 ± 1.9% ~ 107.3 ± 1.2% (n = 3) were obtained in milk and river water samples, respectively. This work demonstrates the promising application of Fe 3 O 4 @3D COF as efficient adsorbents of trace BPA, and opens up a new access for the efficient MSPE in sample pretreatment for food or environmental safety analysis., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Time-consuming or tedious operation in multiple-step process might is the obstacle for efficiently preparing aptamer-affinity monolithic column. Here, a new and facile strategy to prepare aptamer-based hybrid affinity monolith in "one-pot" at room temperature was exploited, in which UV light-initiated free-radical polymerization and "thiol-ene" click reaction were implemented simultaneously. Only 7 min was cost for finishing the polymerization reaction, which was only 1/100 of that for the traditional thermal polymerization. Using ochratoxin A (OTA) as the model analyte, the recipe for photo-initiated polymerization was optimized, and SEM morphology, FTIR, EDS, pore size distribution and specific recognition performance were also studied. Compared with traditional thermal polymerization, the resultant monolith was achieved more facilely and displayed better results such as more homogeneous skeleton structure, higher reaction efficiency of aptamer (>88.2%) and better specific selectivity to OTA. Besides, an extremely low nonspecific adsorption of analogues was obtained and showed a level at only 1/25 of that in the similar aptamer-affinity monolith prepared by thermal polymerization. Applied to beer and red wine samples, good recovery yields about 99.7 ± 4.0% -101.2 ± 2.3% (n = 3)was achieved with the acceptable RSDs. It would open up a rapid and promising access to efficiently preparing high-performance aptamer-based affinity monolithic columns for online specific recognition., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Recently, scientists have reported a range of chiral fluorescence materials or chiral composites that can emit circularly polarized luminescence. Herein, two achiral metal-organic colloidal solutions were studied, showing active circularly polarized luminescence, which is observed in vortex stirring. The absolute values for g lum are 0.05 and 0.03 and the plus or minus sign of g lum depends on the colloidal structure and stirring direction, which make the property easy to manipulate. Further, the host-guest interaction study suggests both electrostatic interactions and coordination bonding may influence the chiroptical property from the colloidal solution to the guest molecule. Rhodamine 6G and its carboxylic acid derivative exhibit good quantum yields and acceptable g lum values in the colloidal solution., (© 2021 Wiley-VCH GmbH.)

In this paper, a novel adsorbent based on aptamer was prepared via "thiol-ene" click chemistry reaction and used for selective adsorbing the trace phthalic acid esters (PAEs) from drinking water and juice samples, which depended on the group selectivity of aptamers to the ester and the benzoyl groups of PAEs. The morphological structures of the obtained adsorbents were characterized by Fourier Transform infrared spectroscopy (FT-IR), fluorescence spectra, Energy Dispersive Spectrometer (EDS), Brunauer-Emmett-Teller (BET). The selectivity of the prepared adsorbent was evaluated and the results showed that the recovery of the adsorbent with aptamer for PAEs was 66.10-108.90%, while the recovery of adsorbent without aptamer was only 32.41-37.59%. The limit of detection (LOD) (S/N = 3) and limit of quantitation (LOQ) (S/N = 10) of PAEs coupled with HPLC-UV were obtained in the range of 0.11-0.88 μg L -1 and 0.22-1.33 μg L -1 , respectively. This work gave a facile and efficient approach to for specific enrichment and highly sensitivity detection of PAEs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Highly specific sample pretreatment for the sensitive detection of trace bisphenol A (BPA) in compliacted samples is critical. Herein, a new protocol towards online specific recognition and sensitive detection of BPA was proposed by using Aptamer@AuNPs-modified affinity monolith coupled with LC-MS. Optimization of polymerization conditions and characterization such as the morphology, energy spectrum, mechanical stability, aptamer coverage density and specific performance of the affinity monolith were studied. Nano-gold particles (AuNPs) densely distributed on the rigid hybrid-silica substrates, and an unusually high aptamer coverage density reached 3388 pmol/μL, which was favorable to fulfill the effective identification of BPA with high selectivity and inhibit the interference of analogs including BPB and BPC. A highly sensitive recognition of BPA was obtained with the limit of detection (LOD) as low as 0.02 ng/mL. Applied to dairy milk products and serum samples, trace BPA could be sensitive detected by this strategy, while the poor response was achieved by using traditional non-specific SPE column for sample pretreatment. Satisfactory recoveries of fortified BPA were measured as 97.45 ± 2.24%-98.03 ± 4.36% (n = 3) in powdered infant formulas, 96.64 ± 3.37% ~ 99.42 ± 3.22% (n = 3) in bottled milk, 94.69 ± 2.15% ~ 100.96 ± 1.94% (n = 3) in boxed milk, and 93.71 ± 1.53% ~ 96.73 ± 2.56% (n = 3) in children serum samples, respectively. This protocol lights a new access to online specific identification of trace BPA from complex matrix with good detection sensitivity by using aptamer-affinity monolithic column., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Via the facile photopolymerization and thiol-ene click chemistry, a hydrophilic polyhedral oligomeric silsesquioxane (POSS)-containing affinity monolithic column with a high load of aptamers and fast preparation was presented, and successfully applied to the efficient specific recognition and sensitive detection of zearalenone (ZEN) by coupling with HPLC. Optimization of polymerization reaction and polymer recipe were studied, and characteristics such as structural morphology, affinity performance and specificity to ZEN were evaluated. A highly hydrophilic POSS-based aptamer affinity monolith was rapidly prepared in 1.1 h, and a high capacity of aptamer reached 2772.61 pmol/μL that was much higher than that of the current POSS-based aptamer affinity monoliths. By this way, the hydrophilic nature and aptamer coverage indensity in POSS monoliths were well improved. The mixed-mode mechanism including aptamer affinity recognition and hydrophilic interaction were employed for the specific analysis of ZEN. Applied to the monitoring of ZEN, a good selective recognition and sensitive detection were obtained with the detection limit (LOD) of 0.02 ng/mL. The stability and reproducibility were acceptable and the intra-day, inter-day and column-to-column relative standard deviations (RSDs) of the ZEN recovery were gained in the range from 2.28% to 5.32%, respectively. Satisfactory recoveries of ZEN in rice samples were realized ad 98.6 ± 2.8%-100.8 ± 2.0%. It might provide a preferable access to online specific analysis of ZEN via the hydrophilic POSS-based affinity monolith with a large capacity of aptamers and a high preparation efficiency., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Sensitive and specific analysis of zearalenone (ZEN) mycotoxin in cereals for ensuring food safety is critical and remains challenging. Herein, a new gold nanoparticles @aptamer-functionalized hybrid affinity monolithic column was proposed and employed for online specific recognition of ZEN by HPLC. Characterization on the morphology, Brunauer-Emmett-Teller (BET) surface area mechanical stability and specific performance of the obtained affinity monolith were investigated. A super-high aptamer coverage density could reach 3636 pmol/μL, which is preferable to gain an effective analysis of ZEN with high specificity and a low interference of co-existed substances including typical α-Zearalenol (α-ZOL) and Aflatoxin B 1 (AFB 1 ). The sensitive recognition of trace ZEN was obtained with the limit of detection (LOD) as low as 0.05 ng/mL. Applied to real cereal samples, satisfactory recoveries were obtained in the range of 91.6 ± 1.4%-97.8 ± 2.6% (n = 3) in corn, 93.8 ± 3.1%-95.0 ± 3.6% (n = 3) in wheat, and 90.9 ± 4.7%-94.7 ± 3.8% (n = 3) in rice, respectively. The results on quantitative analysis were similar to that of LC-MS and better than that obtained by using immunoaffinity column (IAC) or molecularly imprinted polymer (MIP). This protocol provided an efficient access to high-efficient online specific recognition of ZEN in cereals by using such an aptamer-affinity capillary monolithic column., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest. We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled “Towards high-efficient online specific discrimination of zearalenone by using gold nanopaticles@aptamer-based affinity monolithic column”., (Copyright © 2020. Published by Elsevier B.V.)

A functional stainless steel microextraction fiber easily prepared by in situ growing metal-organic framework UiO-66 was presented and used for high-performance analysis of polycyclic musks. Via the robust Ag-SH bonding reaction, mercaptoacetic acid was easily anchored on Ag film to provide carboxyl group on the stainless steel fiber, then in situ grown UiO-66 was fulfilled via the coordination reaction between Zr 4+ and carboxyl group. Good characteristics including large surface area, high thermal stability, and good adsorption property were achieved. Sensitive detection limits (0.015-0.040 ng/L) were achieved for polycyclic musks by coupling with gas chromatography with mass spectrometry, and it could be stable enough for 150 extraction cycles without a significant loss of extraction efficiency. Compared with the classical commercial fibers, 2.2-11.4 times higher enhancement factors were shown. Applied to the analysis of fortified river water samples, five typical polycyclic musks were well detected with the recoveries of 90.2-101.8%, respectively. It showed a facile approach for preparing stainless steel microextraction fiber via chemically bonding in situ grown metal-organic framework for high-performance enrichment., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A facile strategy for highly efficient fabrication of chiral monolithic column was carried out by the simple "one-pot" hydroxymethyl polycondensation of native β-cyclodextrin (β-CD) and urea-formaldehyde (UF). In-situ rapid substitution of native β-CD and efficient polycondensation of β-CD products and UF oligomers was proposed and fulfilled in one pot. The feasibility, mechanism and key parameters of polycondensation reaction were discussed. The data on crosslinking polycondensation and reaction kinetics were further evaluated. Characteristics including the morphologies, permeability and structure stability of the resultant monolithic columns were also studied. Under the optimal conditions, the "one-pot" hydroxymethyl polycondensation was accomplished in an aqueous solution within only 10 mins. Satisfactory stability and repeatability were gained, and good enantioseparation of eight model enantiomers was successfully achieved with the resultant β-CD-based monolith. It was simple and highly efficient, and the organic solvents, special CD derivatives and tediously long-time polymerization reaction were successfully avoided, which might light a new access to rapid preparation of CD-chiral monolith for high-performance enantioseparation., Competing Interests: Declaration of Competing Interest The authors declare no Conflict of Interest., (Copyright © 2019. Published by Elsevier B.V.)

In this study, a double-recognized aptamer-molecularly imprinted monolithic column (Apt-MIP monolithic column) was prepared by introducing both aptamer and MIP to reduce non-specific adsorption. Its preparation parameters such as the time of photo-initiation, the dosage of photo-initiator and the concentration of aptamer were investigated in detail. The recovery ratios of ochratoxin A (OTA) to ochratoxin B (OTB) on Apt-MIP monolithic column, Apt monolithic column and MIP monolithic column were 116.1, 40.8 and 69, respectively. Even if the concentration of OTB was 10 times that of OTA, the recovery of OTB was only about 2.9%. Applied to beer samples, the prepared Apt-MIP monolithic column drastically resisted background adsorption and the high-specificity recognition for OTA was obtained with the recoveries of 95.5-105.9%. This work provided a simple and effective method to selectively identify OTA from complex samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Inspired by the structure and properties of gemini surfactant, a novel amphiphilic gemini-iridium complex (GIC-Ir) has been developed, which can spontaneously form vesicles by self-assembly and exhibit excellent dispersibility and high emission intensity in water. The emission of GIC-Ir can be rapidly and selectively quenched by picric acid (PA) due to the aromatic groups and two long-chain quaternary ammonium (QA) groups with positive charge, which endow GIC-Ir vesicles outstanding capability to capture negatively charged PA, and greatly promote the interaction between GIC-Ir and PA. Theoretical calculations and spectral studied indicated that the photoinduced electron transfer and resonance energy transfer may be responsible to the emission quenching. Furthermore, the real water samples and in vitro studies further prove that GIC-Ir can be used as a promising chemosensor for the detection of PA both in water and intracellular., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Nonspecific adsorption is a challenge of specific recognition on aptamer-based affinity monoliths. Here, a novel highly hydrophilic polyhedral oligomeric silsesquioxane (POSS)-containing aptamer-based hybrid-silica affinity monolith with a good recognition nature was prepared and used for specific discrimination of ochratoxin A (OTA). A homogeneous polymerization mixture consisted of POSS chemicals, hydrophilic monomers and aptamer solution was directly polymerized via the "one-pot" method. Preparation and characterization of the resultant affinity monolith were studied in detail. A highly hydrophilic nature was obtained and the typical hydrophilic interaction liquid chromatography (HILIC) was observed when acetonitrile (ACN) content in mobile phase was 25%, which reached the highest hydrophilicity of POSS-based hybrid monoliths. By using OTA as model analyte, the nonspecific adsorption was effectively suppressed. The recovery of the analogue ochratoxin B (OTB) was only about 0.1% even if the content of OTB was 50 times more than OTA, which was much better than other POSS-containing monoliths and polar siloxane-based hybrid monoliths. Applied to beer samples, the adsorption of background materials was drastically resisted, and efficient recognition of OTA was obtained with the recoveries of 94.9-99.8%. Much less disturbance was observed than that occurred in hydrophobic POSS-based affinity monolith. It lights an attractive implement with high hydrophilicity and specificity for online selective recognition of OTA., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Developing a high-performance modification protocol is critical for efficiently fabricating affinity monolith. Herein, by using 2,4,6-trichloro-1,3,5-triazine as the linker, a simple triazine-bridged approach was proposed for efficiently fabricating aptamer-grafted polyhedral oligomeric silsesquioxane-polyethyleneimine affinity monolith with high specificity toward ochratoxin A. Experimental parameters, column characteristics and specificity performances of the resultant affinity monolith were investigated in detail. Under the optimal conditions, 2,4,6-trichloro-1,3,5-triazine was rapidly grafted on the polyamine matrix, and effectively applied to the subsequent bridge linkage of aptamers. It was simple and effective, which resulted in a significant decrease of modification time, excellent properties including the high coverage density of aptamer up to 1799 pmol/μL and sensitive detection of ochratoxin A as low as 10 pg/mL in beer samples. This protocol provides a facile approach for fabricating aptamer-grafted polyamine affinity monoliths with highly selective discrimination performance., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A strategy on amperometric detection for CZE of phenol carbamates as model analytes with a facile in-line thermal hydrolysis was presented, in which a thermal hydrolysis, subsequent CZE separation and final column-end amperometric detection were accomplished in an intact capillary. Key parameters of hydrolysis dynamics of carbamates and electrochemical detection of the hydrolysates were studied, as well as electrophoretic conditions. Under the optimal conditions, the capillary was utilized as chambers for in situ hydrolysis, CZE separation, and electrochemical detection. The successive separation of hydrolysates of five carbamates (propoxur, carbofuran, 3-OH-carbofuran, carbaryl and bendiocarb) were achieved within 17 min. Applied to vegetable samples, the recoveries of carbamates fortified at 0.02 and 0.05 mg/kg were ranging in 88-107.2 and 86.3-107.3%, respectively. The success in the implementation of such a scheme resulted in a simple instrument as compared with those current analytical methods with post-column derivization or pre-column hydrolysis, or online enrichment in chip, respectively. This protocol might possess a potential utility for the sensitive amperometric detection of phenol carbamates., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Clinical diagnostics and therapeutics of tumors are significantly benefitted by the development of multifunctional theranostic agents, which integrate tumor targeting, imaging, and therapeutics. However, the integration of imaging and therapy functionalities to a unimolecular framework remains a great challenge. Herein, a family of amphiphilic gemini iridium(III) complexes (GIC), Ir1-Ir6, are synthesized and characterized. The presence of quaternary ammonium (QA) groups endows GIC with adjustable water solubility and excellent self-assembly properties. Spectroscopic and computational results reveal that introducing QA groups into cyclometalating ligands (ĈN ligands) can overcome the drawback of aggregation-caused emission quenching and ensure Ir1-Ir3 with high emission intensity and excellent singlet oxygen ( 1 O 2 ) generation ability in aqueous media. Cell-based assays indicate that Ir3 shows higher cellular uptake efficiency and localizes specifically in the mitochondria, as well as exhibits outstanding photostability and an impressive phototoxicity index with satisfactory performance in mitochondria-targeted imaging and photodynamic therapy (PDT) of tumor cells. Furthermore, in vivo studies further prove that Ir3 possesses excellent antitumor activity and remarkably inhibits the growth of the HepG2 cells under PDT treatment. Consequently, this study presents a promising strategy for designing clinical application potential multifunctional iridium complex theranostic agents for mitochondria-targeted imaging and PDT in a single molecular framework.

In this study, a new ionic liquid functionalized cross-linked chitosan (IL-CCS) was prepared and utilized as an adsorbent for removing sunset yellow FCF (SY) from aqueous solutions. The physicochemical properties of the adsorbent were characterized using infrared spectroscopy (IR), scanning electron microscope (SEM), nitrogen adsorption-desorption isotherms and thermogravimetric analysis (TG). The effects of the experimental parameters such as initial pH, the adsorbent dose and contact time on the absorption process of SY on IL-CCS were investigated in detail. The results showed that the adsorption capacity of IL-CCS for SY had no significant differences when pH of the solution changed from 2.0 to 10.0, and the maximum adsorption capacity of IL-CCS was 300.28 mg/g, obviously higher than that of CCS (36.08 mg/g). In addition, the results of adsorption isotherm, kinetic and thermodynamics showed that the adsorption process could fit with Langmuir model, pseudo-second order model, separately. The exothermic nature of the reaction was revealed through thermodynamic parameters. From the above, IL-CCS has a good prospect for treatment of wastewater containing anionic dyes due to high efficiency adsorption during a broad pH range., (Copyright © 2019. Published by Elsevier B.V.)

A novel polyhedral oligomeric silsesquioxane (POSS)-containing aptamer-modified hybrid affinity monolith with excellent hydrophilicity and unique architecture without Si-OH groups is presented herein, and the nonspecific adsorption caused by the hydrophobic nature of the monolithic column or polar interaction with silanol groups is minimized. Via a simple "one-pot" procedure, hydrophilic monomers were facilely polymerized with the POSS-methacryl substituted (POSS-MA) and aptamer; a highly hydrophilic nature was obtained and the lowest contact angle of 11° was achieved. By using ochratoxin A (OTA) as the model analyte, highly selective recognition of OTA in the mixture was achieved and the control of nonspecific interactions and the cross-reactivity of OTB and AFB1 were significantly improved. The recovery yield of OTB caused by nonspecific adsorption in the resultant monolith was only about 0.1% and remained steady even with the coexistence of a high OTB content (OTA : OTB = 1 : 50), which reached the best level to date and was obviously less than the 6.1% occurring in the hydrophobic POSS-containing control monolith, 8.3% in the POSS-PEI@AuNPs@aptamer affinity monolith and 18.7% in the silica-hybrid affinity monolith. When applied to wine and wheat samples, the nonspecific adsorption was significantly reduced and efficient discrimination of OTA was obtained with better results than that of the hydrophobic POSS-containing affinity column. This provides an attractive tool for minimizing the nonspecific adsorption for highly selective on-column recognition.

An organic-silica hybrid monolith was prepared by a single-step ring-opening polymerization of octaglycidyldimethylsilyl polyhedral oligomeric silsesquioxane (POSS-epoxy), polyethylenimine (PEI), and β-cyclodextrin (β-CD) in a ternary porogenic solvent consisting of polyethylene glycol, 1,4-butanediol, and 1-propanol. The framework of POSS-PEI hybrid monolith could offer well-defined 3D skeleton, while β-CD with the ability of forming a host-guest inclusion complexes with a variety of compounds could show an ability of specific selection. The obtained hybrid monoliths were successfully applied for separation of phenols, benzoic acids, and nucleobases. Especially due to the introduction of β-CD, positional isomers including hydroquinone and resorcinol, o-nitrophenol and p-nitrophenol, as well as p-chlorophenol and o-chlorophenol were baseline separated and the column efficiency reached 82 300 plates/m for hydroquinone., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Based on our developed sodium hyaluronate-functionalized urea-formaldehyde (HA-UF) monolith, a silver nanoparticles-coated monolithic column has been fabricated via the interaction between silver nanoparticles (Ag NPs) and HA. The successful coating of Ag NPs on the parent monolith was proven by SEM, EDAX, UV-vis spectrum and XPS. Nitrogen adsorption desorption isotherms and Barret-Joyner-Halenda (BJH) pore size distributions of the parent and resultant monolith were also performed. Due to the Ag + -like affinity interaction caused by the contact of unsaturated compounds and Ag NPs, the Ag NPs-coated monolith showed satisfactory extraction efficiency towards these compounds, and was applied for in-tube solid-phase microextraction (SPME) of monounsaturated fatty acid methyl esters (MUFAMEs). Several factors for in-tube SPME, such as ACN percentage in the sampling solution, elution volume, sampling and elution flow rate, were investigated with respect to the extraction efficiency of model MUFAMEs. Under the optimized SPME conditions, a simple in tube SPME-Ag + -HPLC method for detection of model MUFAMEs has been proposed, the limits of detection (LODs) were less than 5.2 μg/kg, and the recoveries of spiked French fry samples were ranged from 86.6% to 96.1% with relative standard deviations (RSDs) less than 5.2%. This study provided an Ag NPs-coated monolith with good reproducibility and repeatable extraction performance, and developed an efficient method for in-tube SPME of MUFAMEs in practical food samples., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A convenient and high-performance AuNPs@aptamer-modified mercaptosiloxane-based hybrid affinity monolithic column with an unusually high coverage density of aptamers was facilely prepared and used for on-column selective recognition of ochratoxin A (OTA). Due to the high surface-to-volume ratio of AuNPs, the robust conjugation of Au-SH and large specific surface area of hybrid-silica monolith, high coverage density of 5'-SH-aptamers up to 3494 pmol μL-1 was achieved, which was 2.5-10 folds higher than that of other previously reported affinity monoliths modified with AuNPs@Apt. Using OTA as the model analyte, the highly selective recognition of OTA was carried out via online coupling with HPLC, and the cross-reactivity towards analogues, such as OTB and aflatoxin B1, was weak. High recovery yields of OTA were achieved at more than 92% (n = 3) even when OTB was added at a high concentration level up to 50 ng mL-1. For sample analysis, efficient discrimination of OTA was successfully obtained with a sensitive detection limit of 25 pg mL-1. The recoveries of OTA with different fortified levels were achieved at 88.6%-94.1% and 88.2%-94.3% for beer and wine samples, respectively. This protocol provides a facile approach for fabricating a desirable affinity monolith modified with abundant aptamers for highly selective and sensitive on-column extraction of target analyte OTA.

A novel aptamer-based polyhedral oligomeric silsesquioxane (POSS)-containing hybrid affinity monolith has been prepared with a facile "one-pot" process simultaneously via "free radical polymerization" and "thiol-ene" click reaction, and used for on-line selective extraction and practical analysis to trace ochratoxin A (OTA). By using the ternary porogenic mixture composed of water/DMF/PEG, a homogeneous polymerization mixture with POSS chemicals, acrylate-based monomers and aptamer aqueous solution was obtained, and the copolymerization of POSS chemicals, polymer monomers and aptamer aqueous solution was systematically studied. Characterizations such as the morphology, FT-IR and fluorescence spectra, mechanical stability, dynamic binding capacity, cross-reactivity and selectivity of the resultant affinity monolith were also evaluated. Attributed to the porous monolithic structure and aptamer-based affinity interaction, acceptable selective recognition and recovery yields towards trace OTA were obtained. With a 5-fold volume enrichment, the limit of detection (LOD) and limit of quantitation (LOQ) of OTA in fortified beer samples were gained at 0.025 ng/mL (S/N = 3) and 0.045 ng/mL (S/N = 10), respectively. It could be competent for the sensitive measure of actual OTA residues in real beer samples. In comparison with the previously reported strategies containing common "sol-gel" chemistry, the proposed protocol to fabricating aptamer-modified POSS-containing hybrid affinity monolith showed a simpler preparation with acceptable selectivity and higher recovery to trace OTA., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Via the facile ring-opening reaction of epoxy groups with quinine, a novel polymer monolith with quaternary ammonium for reversed-phase/strong anion-exchange mixed-mode has been fabricated for pressurized capillary electrochromatography (pCEC). Optimization on the preparation of quinine-modified monoliths has been investigated, and characteristics including morphology, permeability, mechanical stability, reproducibility, and column performance have been also studied. Active quaternary ammonium groups were conveniently produced to generate cationic action sites and stable anodic electroosmotic flow. Multiple interactions including reversed-phase, strong anion-exchange, electrostatic repulsion and π-π stacking interactions were obtained. Satisfactory separation capability of various analytes such as alkylbenzenes, polycyclic aromatic hydrocarbons, benzoic acid and its homologs, and β 2 -receptor excitants has been achieved. Applied to the real sample, the good resolution of three alkaloids in Corydalis yanhusuo were achieved by pCEC with the quinine-modified monolith. The results light a potential access to facilely fabricating quaternary ammonium-functionalized polymer monolith with multiple interactions for efficient electrochromatography profiling of various compounds., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel hybrid affinity monolith with a high aptamer coverage density was developed via a highly efficient modification of aptamer@gold nanoparticles (Apt@AuNPs) on a well-controlled 3D skeletal POSS-polyethylenimine (PEI) matrix. The effects of amine reagents and the skeletal structures of the hybrid monoliths on the modification efficiency of Apt@AuNPs were studied, and the resultant Apt@AuNPs@POSS-PEI1200 monolith was proposed with a high coverage density of aptamer of up to 1413 pmol μL -1 , which is 4-5 times more than the coverage density when modified with Apt@AuNPs that was reported previously. Characterization including morphology, spectra analysis, mechanical stability, binding capacity and specificity studies was also carried out. Significant specific recognition targeting of ochratoxin A (OTA) was achieved with a detection limit as low as 0.06 ng mL -1 . High recoveries of OTA were achieved of 92.6 ± 1.3% to 94.7 ± 1.4% (n = 3), while the cross-reactivity towards analogues such as ochratoxin B (OTB) and aflatoxin B 1 (AFB 1 ) was weak. This highlights a facile approach to POSS-based affinity monoliths with a high aptamer coverage density for sensitive and selective recognition of a trace target (OTA).

In this work, an organic-inorganic hybrid boronate affinity monolithic column was prepared via "one-pot" process using 4-vinylphenylboronic acid as organic monomer and divinylbenzene as cross-linker. The effects of reaction temperature, solvents and composition of organic monomers on the column properties (e.g. morphology, permeability, and mechanical stability) were investigated. A series of test compounds including small neutral molecules, aromatic amines, and cis-diol compounds were used to evaluate the retention behaviors of the prepared hybrid monolithic column. The results demonstrated that the prepared hybrid monolith exhibited mixed-interactions including hydrophilicity, cation exchange, and boronate affinity interaction. The run-to-run, day-to-day and batch-to-batch reproducibilities of the prepared hybrid monolith for thiourea's retention time were satisfactory with the relative standard deviations (RSDs) less than 0.09, 1.45 and 4.05% (n = 3), respectively, indicating the effectiveness and practicability of the proposed method., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A simple "one-pot" approach for the preparation of a new vinyl-functionalized organic-inorganic hybrid monolithic column is described. In this improved method, the hydrolyzed alkoxysilanes of tetramethoxysilane and triethoxyvinylsilane were used as precursors for the synthesis of a silica-based monolith, while 1-hexadecene and sodium ethylenesulfonate were used as vinyl functional monomers along with azobisisobutyronitrile as an initiator. The effects of reaction temperature, urea content, and composition of organic monomers on the column properties (e.g. morphology, mechanical stability, and chromatographic performance) were investigated. The monolithic column was used for the separation of neutral solutes by reversed-phase pressurized capillary. Furthermore, the monolith can separate various aromatic amines, which indicated its excellent cation-exchange capability and hydrophobic interactions. The baseline separation of the aromatic amines was obtained with a column efficiency of up to 78 000 plates/m., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel sodium hyaluronate-functionalized urea-formaldehyde (UF) monolithic column has been developed by in-situ polycondensation of urea, formaldehyde and sodium hyaluronate (HA). HA plays both the roles of crosslinking and hydrophilic functionalization. The preparation factors including different molecular weights of HA and different amounts of HA were optimized, and then a uniform monolith with satisfactory permeability and hydrophilic binding capacity was obtained. Due to the excellent hydrophilicity of HA, HA-functionalized UF monolith showed higher hydrophilic extraction efficiency than UF monolith, and was applied for hydrophilic in-tube solid-phase microextraction (SPME) of melamine (MEL). Several factors for hydrophilic in-tube SPME, such as ACN percentage in the sampling solution, salt concentration and pH value of the sampling solution, elution volume, sampling and elution flow rate, were investigated with respect to the extraction efficiency of MEL. Under the optimized SPME conditions, the limit of detection (LOD) of MEL was found to be 0.2ng/mL in the milk formula samples, the recoveries of MEL spiked in milk formula samples ranged from 87.3% to 96.7% with relative standard deviations (RSDs) less than 5.1%. Owing to the excellent hydrophilic extraction ability, the novel HA-functionalized UF monolith could provide a promising tool for the sensitive analysis of polar analytes in complicated samples., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A novel urea-formaldehyde (UF) monolithic column has been developed and exploited as a sorbent for hydrophilic in-tube solid-phase microextraction (in-tube SPME) of aminoglycosides (AGs). Because of the innate hydrophilicity, UF monolith showed high extraction efficiency towards these hydrophilic analytes. The adsorption capacities for target compounds dissolved in water/ACN (1:1, v/v) were in the range of 5.18-7.36μg/cm. Due to the lack of a chromophore, evaporative light scattering detector (ELSD) was selected as the detector for AGs, and coupled with the online in-tube SPME-HPLC system. Several factors of the online system, such as trifluoroacetic acid (TFA) and ACN percentage in the sampling solution, ionic strength in the sample solution, elution volume, sampling and elution flow rate, were optimized with respect to the extraction efficiencies. Under the optimized conditions, the limits of detection (LODs) of streptomycin, tobramycin and neomycin were discovered in the range of 3.0-5.2μg/kg. The recoveries were ranged from 82.1 to 96.7% with relative standard deviations (RSDs) of 2.3-5.1% (n=4) at spiking levels of 50, 200 and 500μg/kg, respectively. The excellent applicability of the UF monolithic column was examined by the determination of streptomycin in practical tilapia samples, which showed the potential advantages for the analysis of polar analytes in complicated samples., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Based on in-tube solid-phase microextraction (in-tube SPME) using a hydrophobic poly (octadecyl methacrylate-co-ethylene dimethacrylate) [poly (OMA-co-EDMA)] monolith, a simple high performance liquid chromatography (HPLC) method has been developed for detection of trans-fatty acids (TFAs) as their fatty acid methyl esters (FAMEs). The poly (OMA-co-EDMA) monolithic column with high hydrophobicity was specially prepared for simultaneous microextraction, pre-separation and purification for the analytes. The pre-separation selectivity, the extraction efficiency, and the purification effect for FAMEs were investigated respectively. Furthermore, some operation parameters have been optimized in detail with respect to satisfactory extraction efficiency of the target compounds. Under the optimized conditions, the enrichment factors for model FAMEs were ranged from 58.3 to 70.9, wide linear range (0.01-1.00mg/kg) and low detection limits (LODs) (3.0-7.1μg/kg) were achieved, respectively. In addition, recoveries of the method were in the range from 83.0 to 106.4% with low relative standard deviations (RSDs) of 3.2-4.7% (n=4) at spiking levels of 0.05, 0.25 and 0.5mg/kg, respectively. Finally, the proposed method was successfully applied for detection of TFAs in practical samples, which possesses short time-consuming, low disturbance and high detection sensitivity., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A novel strategy for rapidly fabricating ionic liquid (IL)-bonded multifunctional monolithic stationary phase has been developed by an in-situ polycondensation of urea-formaldehyde (UF) and a lab-made acylamino-functionalized IL (1-acetylamino-propyl-3-methylimidazolium bromide, [AAPMIm]Br). Two polycondensation processes of UF with 1-amino-propyl-3-methylimidazolium bromide or [AAPMIm]Br were evaluated. Several parameters including mass ratio of urea-formaldehyde, amount of [AAPMIm]Br, polycondensation time and reaction temperature were optimized, and the [AAPMIm]Br-bonded monolithic stationary phase could be rapidly synthesized in 10min with a satisfactory permeability and mechanical stability. Used for pressurized capillary electrochromatography (pCEC), a typical hydrophilic interaction (HI) retention could be obtained in the resultant [AAPMIm]Br-bonded monolith when the content of acetonitrile (ACN) in mobile phase exceeded 20%. Multiple retention mechanisms such as hydrophilic interaction (HI), hydrogen bond (HH), anion-exchange and cation-exclude interactions, were acheived in the [AAPMIm]Br-bonded monolith. Various polar compounds including phenols, benzoic acid and its homologues, and enkephalins have been well separated and thus demonstrated a satisfactory separation performance of the obtained monolith. A facile access is lighted for rapid preparation of ionic liquid-bonded monoliths with multiple retention mechanisms for pCEC., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The preparation of porous polymethacrylate-based open tubular capilary columns by in-situ copolymerization of octadecyl methacrylate (OMA), and ethylene dimethacrylate (EDMA) in N,N-dimethylformamide (DMF) solvent are proposed. The parameters of the preparation procedure of the stationary phase are discussed in detail. The surface of the cross-section of an open tubular (OT) column by scanning electron microscope (SEM) showed wrinkle configuration, which is expedient to enhance proportion of stationary phase and column capacity. Efficient separation of six alkyl benzene homologous series (namely, toluene, ethylbenzene, propylbenzene, butylbenzene, amylbenzene and hexylbenzene) were performed by CEC using the prepared column, and their elution order was in agreement with their hydrophobicity. So, the OT columns bonded with octadecyl ligands yielded reversed-phase retention behavior toward nonpolar solutes. In addition, the separation of four antiepileptics was also investigated with satisfactory effectiveness. The column efficiency range was 35 300-49 800 plates/m. The results showed that the C18-OT column of organic matrix for reversed-phase chromatography was successfully prepared via in-situ polymerization in this work. Hereby, this new column thus offers a promising new alternative in OT-CEC and will be useful in separation science.

A novel 1,2-cyclohexylenedinitrilotetraacetic acid (CDTA) modified Fe3O4 magnetic nanoparticles (MNPs) was synthesized by one-step solvothermal method and used as solid phase extraction (SPE) material to preconcentrate trace copper coupled with flame atomic absorption spectrometry (FAAS). The synthesized adsorbents were characterized by field emission scanning electron microscopy and X-ray powder diffraction with a nanoscale. The optimum conditions for the absorption process were investigated on several commonly tested experimental parameters such as pH of the solution, ultrasound time, sample volume, concentration and volume of elution solution. The influences of some anions and cations on the recoveries of Cu(II) ions were also investigated, and no considerable interference was observed. The maximum adsorption capacity of Fe3O4 magnetic nanoparticles and CDTA modified Fe3O4 magnetic nanoparticles were found to be 27.50 mg/g and 78.24 mg/g for Cu(II). The developed method was applied to the determination of Cu(II) in tap and lake water samples with recoveries ranging from 96.4% to 99.1%., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A novel o-phenanthroline-immobilized ionic-liquid-modified hybrid monolith for capillary electrochromatography was synthesized based on chloropropyl-silica, which was prepared by the in situ polymerization of tetramethoxysilane and 3-chloropropyltrimethoxysilane via a sol-gel process. The morphology of the hybrid monolith was characterized by scanning electron microscopy, and relatively stable anodic electroosmotic flow was observed under a broad pH ranged from pH 3.0 to 9.0. The separation mechanism was investigated by separating four neutral molecules (toluene, dimethylformamide, formamide, and thiourea). The obtained hybrid monolith possessed an obviously reversed-phase retention mechanism, but when the acetonitrile content in the mobile phase was >90% v/v, a weak hydrophilic mechanism was observed on the resultant o-phenanthroline-modified chloropropyl-silica hybrid monolith. The reproducibility of the column was also investigated by measuring relative standard deviations of the migration time for four neutral molecules. Relative standard deviations of run to run (n = 3), day to day (n = 3), and column to column (n = 3) were in the range of 0.4-0.7, 0.9-2.1, and 1.4-3.3%, respectively. Basic separations of various polar analytes including phenols and aromatic amines were successfully achieved., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel phenylalanine (Phe) functionalized zwitterionic monolith for hydrophobic electrochromatography was prepared by a two-step procedure involving the synthesis of glycidyl methacrylate based polymer monolith and subsequent on-column chemical modification with Phe via ring-opening reaction of epoxides. Benefitting from the hydrophobicity of both methacrylate-based matrix and aromatic group of Phe, this monolith could exhibit good hydrophobic interaction for the separation. Typical RP chromatographic behavior was observed toward various solutes. The well-controlled cathodic or anodic EOF of the prepared column could be facilely switched by altering the pH values of running buffers. The separation mechanism of this Phe functionalized zwitterionic monolith is discussed in detail. Two mixed-mode mechanisms of RP/cation exchange and RP/anion exchange could be further realized on the same monolith in different pH condition of the mobile phase. Versatile separation capabilities of neutral, basic, and acidic analytes have been successfully achieved in this zwitterionic monolith by CEC method., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel polymeric monolith with hydrophilic interaction and strong anion-exchange mixed-mode has been fabricated for pressurized capillary electrochromatography by an in situ copolymerization of vinylbenzyl trimethylammonium chloride (VBTA) and bisphenol A glycerolate dimethacrylate (BisGMA). The optimization of the polymerization mixture composition has been investigated, and column characteristics in terms of mechanical stability, permeability and reproducibility have been studied in detail. Linear responses between back pressure and flow rate have been achieved in different solvents. The absolute value of swelling propensity (SP) factor for poly(VBTA-co-BisGMA) monolith is 0.41, and the degree of permeability drop from pure ACN to water is about 45%. An acceptable mechanical stability of the column is obtained. The suitable reproducibility is also measured with the RSD for day-to-day (n=3) of retention time and column efficiency less than 3.3%, and the RSD for batch-to-batch (n=3) less than 5.3%, respectively. Under the optimum conditions, the mixed-mode of hydrophilic interaction and strong anion-exchange has been carried out, and efficient electrochromatography profiling of various polar compounds including neutral phenols, negatively charged benzoic acids and positively charged nucleic acid bases and nucleosides are achieved, respectively., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A pyridinium-based immobilized ionic liquid type multifunctional hybrid silica monolith was prepared by the in situ polymerization of 3-chloropropyl-silica matrix and 4,4'-dipyridyl for hydrophilic interaction CEC. The obtained hybrid monolith possessed of high stable skeletal microstructures with obviously hydrophilic retention mechanism under ACN content >50% in the mobile phase. Strong and stable anodic EOF could be observed under a broad pH range from pH 3.0 to 9.0. Due to the immobilized dipyridyl groups bonded to the silica matrix surface, the resulting hydrophilic hybrid monolith possessed multiple separation interactions including hydrogen bond, π-π, and anion exchange. Excellent separations of various polar analytes including electroneutral phenols, charged acid nucleotides, and basic analytes were successfully achieved. The highest column efficiencies up to 120,000, 164,000, and 106,000 plates/m were obtained for nucleotides, nucleic acid bases, and nucleosides and nicotines, respectively. These results demonstrated that the dipyridyl-immobilized ionic liquid functionalized hybrid monolith possessed highly mechanical stability and good chromatographic performance for hydrophilic interaction electrochromatography., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A facile polyhedral oligomeric silsesquioxane (POSS)-based hybrid monolith with multiple mechanisms was developed by an in situ polymerization. High mechanical stability and good separation capabilities to polar and hydrophobic analytes were successfully achieved. An ideal versatile organic-silica hybrid monolith was presented for easy access to the efficient separation of various analytes.

Carboxymethyl chitosan (CMCS) grafted with β-cyclodextrin (CMCS-g-CD) modified silica gel as a new solid phase extraction (SPE) adsorbent for cadmium has been developed. The optimum batch experimental conditions (pH, amount of adsorbent and contact time) and column experimental conditions (concentration and volume of elution solution) were optimized, respectively. The kinetic models for Cd (II) were investigated and the results indicated that pseudo-second-order equation provided a better R(2) (R(2)>0.999) and agreement between calculated Qe value (10.6 mg/g) and the experimental Qe (exp) value (11.3 mg/g). The developed method was successfully applied to the determination of Cd(II) in lake water and tap water with recoveries ranging from 96.0% to 102.0%., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A highly sensitive capillary electrophoretic profiling of nicotine (NIC) and nornicotine (NNIC) was developed and applied to mushrooms with amperometric detection (AD). Effects of the experimental factors including detection potential, separation parameters, and sample pretreatment conditions were investigated. Under the optimal conditions, the electrophoretic analysis of NIC and NNIC was achieved within 8 min on a pencil carbon disc working electrode at 0.95 V, which was lower than those reported previously. Good calibration curves were obtained in 0.01-2.0 μg/mL and 0.02-3.0 μg/mL with the LOD of 2 ng/mL and 5 ng/mL for NIC and NNIC, respectively. The feasibility of the resultant method was verified. Average recoveries of different fortified levels ranged in 80.7-86.0% and 94.0-98.6% for NNIC and NIC were gained, respectively. Applied to a range of mushrooms (Boletus edulis and Lentinus edodes), the NIC contained naturally was successfully found in the level of 19.71-79.20 μg/kg. The results obtained with CE-AD method were acceptable and close to that of HPLC-MS., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel open-tubular CEC column coated with chitosan-graft-(β-CD) (CDCS) was prepared using sol-gel technique. In the sol-gel approach, owing to the 3D network of sol-gel and the strong chemical bond between the stationary phase and the surface of capillary columns, good chromatographic characteristics and unique selectivity in separating isomers were shown. The column efficiencies of 55,000∼163,000 plates/m for the isomeric xanthopterin and phenoxy acid herbicides using the sol-gel-derived CDCS columns were achieved. Good stabilities were demonstrated that the RSD values for the retention time of thiourea and isoxanthopterin were 1.3 and 1.4% (run to run, n = 5), 1.6 and 2.0% (day to day, n = 3), 2.9 and 3.1% (column to column, n = 3), respectively. The sol-gel-coated CDCS columns have shown improved separations of isomeric xanthopterin in comparison with CDCS-bonded capillary column., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new ion-imprinted carboxymethyl chitosan-functionalized silica gel sorbent was synthesized by surface imprinting technique using Cd(II) as the template, carboxymethyl chitosan (CMCS) as the functional monomer and glutaraldehyde as the cross-linking agent for the selective adsorption of Cd(II) from aqueous solution. The optimum batch experimental conditions (pH, amount of adsorbent, contact time) and column experimental conditions (concentration and volume of elution solution) were evaluated. The maximum static adsorption capacity of the ion-imprinted sorbent for Cd(II) was 20.7 mg/g. The enrichment factor of Cd(II)-imprinted polymer for Cd(II) was 257. The relative selectivity factor values of Cd(II)/Pb(II), Cd(II)/Co(II) were 5.3 and 1.5, respectively. The recoveries of water samples were about 98.0-104.0% (R.S.D. ≤ 0.8). The proposed method was successfully applied to determination of Cd(II) in water samples with satisfactory., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A hydrophilic versatile polymeric monolith with multiple retention mechanisms including hydrogen-bonding, π-π and electrostatic interactions, was developed by a simple one-step in situ polymerization. High mechanical stability and excellent separation capabilities of various nonpolar and polar analytes were successfully achieved and employed for multiple separations in mixed-mode chromatography.