Monolithic Capillary Research Articles

Immobilization of controlled Pu:Am ratio on actinide-specific affinity monolith support developed in capillary and coupled to inductively coupled plasma mass spectrometry.

The objective of this work was to develop an actinide-specific monolithic support in capillary designed to immobilize precise Pu:Am ratios and its coupling to inductively coupled plasma mass spectrometry (ICP-MS) for immobilized metal affinity chromatography applications. This format offers many advantages, such as reducing the sample amount and waste production, which are of prime importance when dealing with highly active radioelements. Four organic phosphorylated-based monoliths were synthesized in situ through UV photo-polymerization in capillary and characterized. The capillary coupling to ICP-MS was set up in conventional laboratory using Th and Sm as chemical analogues of Pu and Am. A dedicated method was developed to quantify online Th and Sm amounts immobilized on the monolithic capillaries, allowing to select the best monolith candidate poly(BMEP-co-EDMA)adp. By precisely adjusting the elemental composition in the loading solutions and applying the developed quantification method, the controlled immobilization of several Th:Sm molar ratios onto the monolith was successful. Finally, the capillary ICP-MS coupling was transposed in a glove box and by applying the strategy developed to design the monolithic support using Th and Sm, the immobilization of a 10.5 ± 0.2 (RSD = 2.3%, n = 3) Pu:Am molar ratio reflecting Pu ageing over 48years was achieved in a controlled manner on poly(BMEP-co-EDMA)adp. Hence, the new affinity capillary monolithic support was validated, with only hundred nanograms or less of engaged radioelements and can be further exploited to precisely determine differential interactions of Pu and Am with targeted biomolecules in order to better anticipate the effect of Am on Pu biodistribution.

A novel chiral monolithic nano-column with 50 µm i.d. for the enantioseparation of chiral drugs by nano-liquid chromatography

A novel chiral monolithic nano-column was developed for the enantioseparation of chiral drugs by nano-liquid chromatography (nano-LC). The monolithic capillary with 50 µm i.d. was first prepared by an in-situ polymerization using butyl methacrylate (BuMA), ethylene dimethacrylate (EDMA) and NFMoc-Lysine modified GO nanoparticles. The final monolithic stationary phase was characterized by using FT-IR spectra of synthesized structures, scanning electron microscopy (SEM) and chromatographic analyses. After characterization, the prepared chiral monolithic column was investigated for the chiral separation of pharmaceutical racemates, including anti-inflammatory drugs (e.g., ketoprofen, ibuprofen, naproxen, etodolac and flurbiprofen) and β-blockers (e.g. propranolol, metoprolol and atenolol). It was demonstrated that NFMoc-Lysine modified GO nanoparticles incorporated chiral monolith could be successfully developed while this chiral monolith allowed sensitive chiral separation of chiral drugs. The chiral separation could be mostly achieved via the formation of π-π interactions as well as hydrophilic interactions between chiral stationary phase and enantiomers

Characterization of hybrid organo-silica monoliths for possible application in the gradient elution of peptides.

We characterized thermally polymerized organo-silica hybrid monolithic capillaries to test their applicability in the gradient elution of peptides. We have used a single-pot approach utilizing 3-(methacryloyloxy)propyltrimethoxysilane (MPTMS), ethylene dimethacrylate (EDMA), and n-octadecyl methacrylate (ODM) as functional monomers. The organo-silica monolith containing MPTMS and EDMA was compared with the stationary phase prepared by adding ODM to the original polymerization mixture. Column prepared using a three-monomer system provided a lower accessible volume of flow-through pores, a higher proportion of mesopores, and higher efficiency. We utilized isocratic and gradient elution data to predict peak widths in gradient elution. Both protocols provided comparable results and can be used for peptide peak width prediction. However, applying gradient elution data for peak width prediction seems simpler. Finally, we tested the effect of gradient time on achievable peak capacity in the gradient elution of peptides with a column prepared with a three-monomer system providing a higher peak capacity. However, the performance of hybrid organo-silica monolithic stationary phases in gradient elution of peptides must be improved compared to other monolithic stationary phases. The limiting factor is column efficiency in highly aqueous mobile phases, which needs to be focused on.

Covalent organic frameworks based hierarchical porous hybrid monolithic capillary: Synthesis, characterization, and applications in trace metals analysis

The preparation of hierarchical porous monolithic column with high covalent organic frameworks (COF) loading and micropores accessibility is challenging due to the easy aggregability and sedimentation of COFs. Herein, a novel strategy based on high internal phase emulsion (HIPE) polymerization was proposed for preparing COF hybrid capillary monolithic column with hierarchical porosity. COFs with different frameworks including imine COFs (COF-OMe, COF-F and COF-SH), triazine COF (CTF-1) and boron-based COF (COF-5) were selected to investigate the universality of the preparation strategy. The presence of COF in the monolithic capillary was confirmed by scanning electron microscope, X-ray diffraction and fourier transform infrared spectroscopy. Nitrogen adsorption/desorption experiments and thermogravimetric analysis showed that the prepared COF hybrid monolithic capillary exhibited high COF loading (e.g., 28.7% for COF-SH) and accessibility (e.g., 98.5% for COF-SH), mainly due to the thin walls of void-window structures originated from polymerization of HIPE. The successful preparation of water-stable COF-F, COF-OMe, COF-SH and CTF-1 hybrid monolithic columns demonstrated the proposed synthesis strategy is universal to water-stable COF without tedious optimization of dispersion system, effectively avoiding the sedimentation of COF in pre-polymerization solution. Then, the sulfhydryl-modified COF hybrid polymer (poly(COF-SH-HIPE)) monolithic column was evaluated for the extraction of heavy metal ions, and a method based on poly(COF-SH-HIPE) monolithic capillary microextraction on-line coupled with inductively coupled plasma mass spectrometry detection was developed for analysis of trace Cd, Hg and Pb in human fluid samples.

Lipase as a Chiral Selector Immobilised on Carboxylated Single-Walled Carbon Nanotubes and Encapsulated in the Organic Polymer Monolithic Capillary for Nano-High Performance Liquid Chromatography Enantioseparation of Racemic Pharmaceuticals.

Herein, we report the preparation of lipase immobilised on single-walled carbon nanotubes (SWCNTs) as an enantioselector for capillary monolithic columns and their application in the chiral separation of racemic pharmaceuticals. The columns were prepared through the encapsulation of functionalised SWCNTs (c-SWCNTs) within an organic monolithic polymer, followed by the immobilisation of lipase over the obtained monolith, over a three-day (L1) and five-day (L2) period. The prepared columns were tested for the enantioselective nano-HPLC separation of 50 racemic drugs. A suitable resolution was achieved for 25 drugs using nano-RP-HPLC conditions for both the L1 and L2 capillaries, while no specific resolution was detected under normal-phase HPLC conditions. The developed c-SWCNT-lipase-based polymeric monolithic capillaries are a promising expansion for separating pharmaceutical enantiomers' using nano-HPLC.

Mixed-mode chromatographic performance using nicotinic acid-functionalized chito-oligosaccharide-bonded Ti/Si hybrid monolithic capillary columns.

This article describes the fabrication of porous nicotinic acid-functionalized chito-oligosaccharide-bonded titania/silica hybrid monoliths (TiO2/SiO2@ChO-N) through a co-gelation sol-gel process. A capillary monolith with a well-defined and homogeneous structure was obtained by controlling the hydrolysis speed of titanium alkoxides in a sol mixture by using glycerol and acetylacetone. As a result of the functionalization with chito-oligosaccharides (ChO)-modified nicotinic acid, the obtained stationary phase provides superior physiochemical properties, such as a cationic hydrophilic surface, porosity, and mechanical strength. Scanning electron microscope and attenuated total reflectance-infrared spectroscopy were used to characterize the functionalized monolithic columns. The produced capillary columns showed high chromatographic performance with acceptable selectivity for charged analytes as well as organic polar compounds such as nucleic bases, nucleosides, carbamate pesticides, and strobilurinfungicides. The obtained results also indicated that the functionalized ChO's amino, amide, hydroxyl, and pyridinium ring moieties served as hydrophilic electrostatic traps for charged substances, in addition tostroing π-π interaction with the carbamate pesticides and strobilurin fungicides analytes via hydrogen bonding.

Monolithic 3D structural-substrate SERS sensing platform for ultrasensitive and highly-specific analysis of trace bisphenol A

Constructing advanced substrates with excellent features is promising for sensitive surface-enhanced Raman spectroscopy (SERS) detection. Here a novel capillary monolithic 3D structural-substrate SERS platform with Au@cDNA@Ag@Cyanine 3-aptamer nanoparticles (Au@cDNA@Ag@Cy3-Apt NPs) was fabricated for rapid, highly specific profiling of ultra-trace Bisphenol A (BPA). The proposed SERS platform combined both in-capillary SERS and aptamer-affinity recognition strategies, in which the superior SERS properties of Au–Ag NPs, aptamer selectivity, and the advantages of capillary monolith were integrated. A 3D hierarchically porous network was constructed in the monolithic column, which was endowed with rich hotspots for SERS, rapid sample permeation, and better analysis efficiency than most plane-shaped SERS modes. By varying the amount of Ag+ precursor, the Ag-shell thickness on SERS was finely tuned to guarantee Cy3 label in proximity to the plasmonic surface. Based on the biorecognition of aptamer, the selective identification of BPA occurred and exhibited a significant change in SERS intensity without obvious interference. As a result, the monolithic SERS platform featured facile operation, excellent specificity, and rapid analysis (10 min, much less than the solution-based or planar substrate SERS modes). Ultra-high sensitivity and robust reproducibility for BPA analysis was achieved with a low limit of detection (LOD) at 9.12 × 10-4 ng/L. The feasibility of this SERS platform for monitoring BPA in water and milk samples was also validated. This work lights a new access to capillary monolithic SERS-sensing platform for ultrasensitive and specific analysis of BPA.

In‐tube solid‐phase microextraction (sulfopropyl methacrylate‐co‐ethylene glycol dimethacrylate monolithic capillary) coupled to LC–MS/MS to determine beta amyloid peptides in Alzheimer's cerebrospinal fluid samples

AbstractAlzheimer's disease (AD) is a neurodegenerative disorder characterized by an extracellular accumulation of amyloid beta peptides in the brain. The concentration of the amyloid beta peptides in cerebrospinal fluid (CSF) have been evaluated as potential biomarkers of AD for early diagnostic. In this work, an in‐tube solid‐phase microextraction (in‐tube SPME) coupled to UHPLC–MS/MS method was established to determine amyloid beta peptides in CSF samples from AD patients. A strong cation‐exchange (sulfopropyl methacrylate‐co‐ethylene glycol dimethacrylate) monolithic capillary was synthesized on the inner surface of a fused silica capillary and used as an extractive phase for in‐tube SPME. The morphology and chemical structure of the monolithic phase were characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The proposed method presented linear range from the lower limits of quantification 0.6 and 0.8 to 10 ng mL−1. Excluding the lower limits of quantification values, the analytical validation showed precision with the coefficient of variation values lower than 13.1%, and accuracy with relative standard deviation lower than 13.5%. The in‐tube SPME coupled to UHPLC–MS/MS method was successfully applied to determine amyloid beta peptides in CSF samples from AD patients.

Ni(II) functionalized polyhedral oligomeric silsesquioxane based capillary monolith for purification of histidine-tagged proteins by immobilized metal affinity micro-chromatography

A new capillary monolithic stationary phase was synthesized for the purification of histidine tagged proteins by immobilized metal affinity micro-chromatography (μ-IMAC). For this purpose, mercaptosuccinic acid (MSA) linked-polyhedral oligomeric silsesquioxane [MSA@poly(POSS-MA)] monolith 300 μm in diameter was obtained by thiol-methacrylate polymerization using methacryl substituted-polyhedral oligomeric silsesquioxane (POSS-MA) and MSA as the thiol functionalized agent in a fused silica capillary tubing. Ni(II) cations were immobilized onto the porous monolith via metal-chelate complex formation with double carboxyl functionality of bound MSA segments. μ-IMAC separations aiming the purification of histidine tagged-green fluorescent protein (His-GFP) from Escherichia coli extract were carried out on Ni(II)@MSA functionalized-poly(POSS-MA) [Ni(II)@MSA@poly(POSS-MA)] capillary monolith. His-GFP was succesfully isolated by μ-IMAC on Ni(II)@MSA@poly(POSS-MA) capillary monolith with the isolation yield of 85 % and the purity of 92 % from E. coli extract. Higher His-GFP isolation yields were obtained with lower His-GFP feed concentrations and lower feed flow rates. The monolith was used for consecutive His-GFP purifications with a tolerable decrease in equilibrium His-GFP adsorption over five runs.

Simulation of a Steady‐State Continuous Catalytic Reactive Distillation Column by Using a Multiscale Capillary Model

AbstractA continuous packed‐bed catalytic reactive distillation column used to study the esterification of acetic acid with methanol to synthesize methyl acetate was modeled as a capillary monolith. The solid catalyst used for this study was Indion 180 ion‐exchange resin. The catalyst was immobilized in the column by using a structured packing equivalent to Katapak‐S. Experiments were performed under different operating conditions. To validate the experimental results, a capillary model was developed for the catalytic reactive distillation by combining a model based on evaporation rate with the pore diffusion model for the reaction kinetics at the catalyst‐particle scale. The model predictions for composition and temperature profiles along the length of the column were compared with the experimental data and found to be in good agreement.

Selection and characterization of DNA aptamers for highly selective recognition of the major allergen of olive pollen Ole e 1

In this study, single-stranded DNA aptamers with binding affinity to Ole e 1, the major allergen of olive pollen, were selected using systematic evolution of ligands by exponential enrichment (SELEX) method. Binding of the aptamers was firstly established by enzyme-linked oligonucleotide assay (ELONA) and aptaprecipitation assays. Additionally, aptamer-modified monolithic capillary chromatography was used in order to evaluate the recognition of this allergenic protein against other non-target proteins. The results indicated that AptOle1#6 was the aptamer that provided the highest affinity for Ole e 1. The selected aptamer showed good selective recognition of this protein, being not able to retain other non-target proteins (HSA, cyt c, and other pollen protein such as Ole e 9). The feasibility of the affinity monolithic column was demonstrated by selective recognition of Ole e 1 in an allergy skin test. The stability and reproducibility of this monolithic column was suitable, with relative standard deviations (RSDs) in retention times and peak area values of 7.8 and 9.3%, respectively (column-to-column reproducibility). This is the first study that describes the design of an efficient DNA aptamer for this relevant allergen.

A Polymer-based Monolithic Capillary Column with Polymyxin-B Chiral Selector for the Enantioselective Nano-High Performance Liquid Chromatographic Pharmaceutical Analysis

Herein, we report the first use of Polymyxin-B antibiotic as a enantio-selector in polymer monolithic capillary. The capillaries were functionalised, characterized and tested for the enantioselective nano-HPLC separation of 50 racemic pharmaceutical drugs. They have been easily prepared by immobilizing Polymyxin-B over the organic polymer for 48 h (P1) or encapsulating Polymyxin-B within the organic polymer (P2) and tested for the enantioselective resolution of racemic drugs. Acceptable resolution was achieved for 21 drugs using RP-HPLC conditions on both (P1) and (P2) capillary columns, while no separation was observed under NP-HPLC conditions. Polymyxin-B is commercially available, easily solubilized and stable in both acidic and neutral media. The developed Polymyxin-B-based polymer monolithic capillaries provide a promising expansion of platform in enantioselective HPLC separations.

In situ photo-initiatedpolymerized oligonucleotide-functionalized hydrophilic capillary affinity monolith for highly selective in-tube microextraction of ochratoxin A mycotoxin.

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 7min was required for the rapid polymerization of aptamer-based affinity monolith, which was much less than the reaction time of most thermal polymerization (12-16h) and sol-gel chemistry methods (up to 52h). 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 0.05-50.00ng·mL-1 witha limit of detection (LOD, S/N= 3) of 0.012ng·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.

Rapid Analysis of Biological Samples Using Monolithic Polymer-Based In-Tube Solid-Phase Microextraction with Direct Mass Spectrometry.

Online coupling in-tube solid-phase microextraction (SPME) with mass spectrometry (MS) was achieved by directly utilizing a monolithic SPME capillary as the electrospray emitter. A porous organic polymer with a highly porous structure can not only provide excellent extraction efficiency due to its high specific surface area but also increase the ionization efficiency and stability by producing smaller electrospray droplets. This online coupling strategy significantly simplifies the device as well as the operation process. The whole analytical process only takes about 12 min with a sample amount of 100 μL. By choosing an ionic liquid-based organic polymer with high extraction ability and good stability and adjusting a suitable porous structure for better electrospray, the developed in-tube SPME-MS method showed excellent extraction performance and good reusability without clogging events. As a proof of concept, the proposed method was applied for the analysis of non-steroid anti-inflammatory drugs in plasma and urine samples. The method showed a wide linear range (0.1-200 ng/mL), good linearity (R2 ≥ 0.99), and good reproducibility (intra-day relative standard deviations (RSDs) <3.00% and inter-day RSDs <6.29%).

Daptomycin: A Novel Macrocyclic Antibiotic as a Chiral Selector in an Organic Polymer Monolithic Capillary for the Enantioselective Analysis of a Set of Pharmaceuticals.

Daptomycin, a macrocyclic antibiotic, is here used as a new chiral selector in preparation of chiral stationary phase (CSP) in a recently prepared polymer monolithic capillary. The latter is prepared using the copolymerization of the monomers glycidyl methacrylate (GMA) and ethylene glycol dimethacrylate (EGDMA) in the presence of daptomycin in water. Under reversed phase conditions (RP), the prepared capillaries were tested for the enantioselective nanoliquid chromatographic separation of fifty of the racemic drugs of different pharmacological groups, such as adrenergic blockers, H1-blockers, NSAIDs, antifungal drugs, and others. Baseline separation was attained for many drugs under RP-HPLC. Daptomycin expands the horizon of chiral selectors in HPLC.

Supported Metal Nanoparticles in Metal‐Organic Monoliths for Assembly of a Catalytic Microfluidic Reactor

AbstractA novel strategy has been developed to fabricate an Au@CrADC (ADC=5‐aminobenzene‐1,3‐dicarboxylate) metal‐organic monolithic capillary in microfluidic reactors. Monolithic Cr3+‐based metal‐organic gel (MOG) as catalyst support is synthesized inside fused‐silica capillary employing a two‐step procedure including surface modification of carboxyl group to provide anchoring sites and subsequent MOG formation. Subsequently, Au nanoparticles are in situ immobilized in the monolithic MOG support as active catalysts. The resulting Au@CrADC monolithic capillary is used to assemble a catalytic microfluidic reactor. The catalytic activity of the Au@CrADC reactor is probed by using the oxidative alkyne coupling reaction to synthesize 1,3‐diynes. The catalytic microfluidic reactor demonstrates significantly enhanced catalytic activity in comparison with the corresponding reactions under batch conditions. Additionally, the microfluidic reactor shows high stability with no significant catalytic deactivation during repeated uses.

Aminopropyl hybrid silica monolithic capillary containing mesoporous SBA-15 particles for in-tube SPME-HILIC-MS/MS to determine levodopa, carbidopa, benserazide, dopamine, and 3-O-methyldopa in plasma samples

This manuscript describes an automated method that combines the selectivity of in-tube solid-phase microextraction (in-tube SPME) with the sensitivity of liquid hydrophilic interaction chromatography-tandem mass spectrometry (HILIC-MS/MS) to determine levodopa, carbidopa, benserazide, dopamine, and 3-O-methyldopa in plasma samples. An aminopropyl hybrid silica monolithic capillary containing mesoporous Santa Barbara Amorphous (SBA-15) particles for in-tube SPME was prepared by sol-gel reactions (one step). The organic–inorganic hybrid silica monolithic capillary was reused over fifty times without significant extraction efficiency loss, which attested to its robustness. The FTIR spectra displayed readily identifiable peaks that were characteristic of aminopropyl groups. SEM and TEM micrographs showed that the monolithic phase consisted of a homogeneous, continuous, and mesoporous skeleton composed of interconnected ordered particles. The developed method afforded adequate linearity at concentrations ranging from the lower limit of quantification (1.2–170 ng mL−1) to the upper limit of quantification (2000 ng mL−1), and the coefficients of correlation (r) were higher than 0.99. The method was validated with intra-day and inter-day precision and accuracy. In-tube SPME-HILIC-MS/MS was successfully developed to determine levodopa, carbidopa, benserazide, dopamine, and 3-O-methyldopa in plasma samples obtained from patients with Parkinson’s Disease for therapeutic drug monitoring purposes.

Cotton thread modified with ionic liquid copolymerized polymer for online in-tube solid-phase microextraction and HPLC analysis of nonsteroidal anti-inflammatory drugs.

Cotton fiber is a biodegradable material that possesses properties such as high specific area, adjustable shape, and hygroscopicity. In this work, organic polymer was directly in situ grown on the surface of cotton thread and packed into a poly(ether ether ketone) tube for online in-tube solid-phase microextraction. The novel strategy solves the problems like high backpressure and tedious optimization process of normal monolithic polymer-based in-tube solid-phase microextraction capillary. The quaternary ammonium typed ionic liquid of 1-allyl-methylimidazolium chloride, 4-vinylbiphenyl, and ethylene dimethacrylate were co-polymerized and in situ grown on the surface of cotton thread as extraction phase. The solid-phase microextraction tube showed excellent performance for the extraction of three nonsteroidal anti-inflammatory drugs including ketoprofen, naproxen, and flurbiprofen due to the strong ion exchange and hydrophobic interactions. After online coupling with a high-performance liquid chromatography system by six-port valve, the method was applied for the quantitative analysis of nonsteroidal anti-inflammatory drugs in human plasma samples showing good enrichment performance (enrichment factor between 263 and 279), high sensitivity, good linearity, and good reproducibility.

Determination of Monoaromatic Hydrocarbons in Water Samples by Nano-Liquid Chromatography using a Composite Carbon Nanotubes- Lauryl Polymethacrylate Capillary Monolithic Column

Background: This work reports a green analytical method for the determination of organic environmental pollutants using nano-liquid chromatography with a self-made column for rapid, sensitive, inexpensive and efficient analysis of BTX pollutants in water. The applications of monolithic nanoscale columns for quantitative analysis of environmental real samples are very limited in the literature. Methods: A capillary column containing a composite of multi-walled carbon nanotubes incorporated into a lauryl methacrylate-co-ethylene dimethacrylate porous monolithic polymer was fabricated for the determination of BTX pollutants in real water samples. Results: Baseline separation was accomplished at 0.4 µL/min flow rate with UV-detection set at 208 nm. Under the optimum conditions, the calibration curves were validated over the range of 1.0-500 µg/L with R2 more than 0.9992. The detection limits of benzene, toluene, o-xylene and m/p-xylene were 0.25, 0.05, 0.075 and 0.05 µg/L, respectively. After a simple extraction process with a theoretical preconcentration factor equal to 200, the recovery values in Milli-Q, tap and sea water samples were found to be ranged from 84.85 to 97.84% with %RSD less than 7.5. Furthermore, we reported a comparison between our prepared composite column with a commercial C18 silica based column which is the most used in such analytical field. Each column demonstrated its advantages from different analytical aspects. Conclusion: The application of monolithic columns and nano-scale LC for routine analysis of environmental samples is very promising as the use of monolithic capillary columns offers several advantages over conventional scale particulate packed columns.

Online simultaneous speciation of ultra-trace inorganic antimony and tellurium in environmental water by polymer monolithic capillary microextraction combined with inductively coupled plasma mass spectrometry

Poly(glycidyl methacrylate-ethylene dimethacrylate) monolithic capillary was functionalized with cystamine, and the resultant mercapto functionalized polymer monolithic capillary was investigated for the separation of Sb(III) and Sb(V) as well as Te (IV) and Te(VI). It was found that Sb(III) and Te(IV) were selectively retained on the prepared monolithic capillary over a wide pH range (1–8), while Sb(V) and Te(VI) were not be adsorbed in the pH range of 3–8. Based on it, a method of capillary microextraction online hyphenated with ICP-MS was proposed for simultaneous speciation of trace inorganic Sb and Te. Sb(V) and Te(VI) were pre-reduced simultaneously into Sb(III) and Te(IV) and subjected to the proposed method to get the information of total Sb and Te; the content of Sb(V) and Te(VI) was calculated by subtracting Sb(III) and Te(IV) from total Sb and Te. Under the optimized conditions, the limits of detection for Sb(III) and Te(IV) were 3.9 and 5.9 ng L−1 with the relative standard deviations of 5.2 and 4.1% (c = 0.1 μg L−1, n = 7), respectively. The accuracy of the method was verified by Certified Reference Materials of Environmental Water (GSB07–1376-2001, GBW(E)080548). In real water samples analysis, sub-μg L−1 of Sb(V)/(III) was found in the Yangtze River and East Lake water, and the recoveries for the spiked real water samples for Sb(V)/(III) and Te(IV)/(VI) were 87.0–113% and 83.5–107%, respectively. The proposed approach was rapid, sensitive and exhibited great application potential in the simultaneous speciation of inorganic Sb and Te in environmental waters.