Characterization and cytocompatibility of polydopamine on MAO‐HA coating supported on Mg‐Zn‐Ca alloy

Magnesium has been suggested as a potential biodegradable metal for the usage as orthopaedic implants. However, high degradation rate in physiological environment remains the biggest challenge, impeding wide clinical application of magnesium‐based biomaterials. In order to reduce its degradation rate and improve the biocompatibility, micro‐arc oxidation coating doped with HA particles (MAO‐HA) was applied as the inner coating, and polydopamine (PDA) film was synthesized by dopamine self‐polymerization as the outer coating. The microstructure evolution of the coating was characterized using scanning electron microscopy (SEM), atomic force microscope (AFM), X‐ray diffraction analyses (XRD), Fourier transform infrared spectroscopy (FT‐IR), and X‐ray photoelectron spectroscopy (XPS). The results showed that PDA film had covered the entire surface of MAO‐HA coating and the pore size of MAO‐HA coating decreased. The root mean square (RMS) roughness of PDA/MAO‐HA coatings was approximately 106.46 nm, which was closer to the optimum surface roughness for cellular attachment as compared with MAO‐HA coatings. Contact angle measurement indicated that the surface wettability had been transformed from hydrophobic to hydrophilic due to the introduction of PDA. The PDA/MAO‐HA coatings exhibited better corrosion resistance in vitro, with the self‐corrosion potential increasing by 150 mV and the corrosion current density decreasing from 2.09 × 10^?5 A/cm ² to 1.46 × 10^?6 A/cm ² . In hydrogen evolution tests, the corrosion rates of the samples coated with PDA/MAO‐HA and MAO‐HA were 4.40 and 5.95 mm/y, respectively. MTS assay test and cell‐surface interactions experiment demonstrated that PDA/MAO‐HA coatings exhibited good cellular compatibility and could promote the adhesion and proliferation of MC3T3‐E1 cells.     

Micro‐arc oxidation and electrophoretic deposition of nano‐grain merwinite (Ca3MgSi2O8) surface coating on magnesium alloy as biodegradable metallic implant

Magnesium alloys are promising biomaterials as biodegradable implant for orthopedic applications. However, their low corrosion resistance and poor bioactivity have prohibited their implant applications. In order to enhance these two properties, a nano‐grain merwinite coating was prepared on magnesium alloy. Its corrosion and the bioactivity behavior were characterized with electrochemical and immersion tests. The results showed that the nano‐grain merwinite coating can improve both the corrosion resistance and the bioactivity of the magnesium alloy making it an appropriate material for biodegradable bone implants. Copyright © 2014 John Wiley & Sons, Ltd.     

Effects of anodic oxidation on corrosion properties of Al coating by arc spraying in seawater

A layer of Al coatings was prepared on the S355 steel by arc spraying, which was conducted by anodic oxidation treatment; the morphologies, chemical element compositions and phases of Al coating, and anodic oxide layer were analyzed with field emission scanning electron microscope (FESEM), energy dispersive spectrometer (EDS) and X‐ray diffraction (XRD), respectively. The corrosion protections of Al coating before and after anodic oxidation were discussed with a seawater immersion test; the corrosion resistance mechanisms of Al coating and anodic oxide layer in the seawater were also investigated. The results show that the thickness of Al coating is about 300 µm by arc spraying, the sample surfaces become loose after seawater immersion corrosion and Cl^? and O^2? penetrate into the substrate from the cracks, destroying the binding properties of coating–substrate, and the coating fails. After anodic oxidation, the oxide layer is formed in the surface of Al coating with the thickness of about 30 µm; the corrosion products are mainly composed of Al(OH)₃, which barraged the holes caused by seawater corrosion. The corrosion cracks are formed during the corrosion, while the number and depth of cracks decrease obviously after anodic oxidation treatment. The corrosion of Al coating becomes the local corrosion after anodic oxidation treatment, and the grains are smaller, which are easily nucleated to form a new corrosion resistance layer. Copyright © 2015 John Wiley & Sons, Ltd.     

Polystyrene‐grafted Al surface with excellent superhydrophobicity and corrosion resistance

A superhydrophobic Al surface was successfully fabricated by a facile and environmentally friendly method as the boiling water treatment and 3‐glycidoxypropyl trimethoxysilane (GPS) as well as carboxyl‐terminated polystyrene (PS‐COOH) modification. The fabrication procedure, morphology, composition, and corrosion resistance of the superhydrophobic Al surface were investigated. Results show that the treatment in the boiling water endows the Al surface with the porous and roughened structure, while the modification with GPS as well as PS‐COOH grafts the long PS chains onto the micro‐scale and nano‐scale hierarchical structure. Consequently, a superhydrophobic Al surface with a contact angle of 153.6° and a rolling angle of 3° is obtained. Additionally, a vast majority of surface area is covered by the air in the solid–liquid contact area for the superhydrophobic Al surface, and which can prevent the corrosive ions entering into the Al surface. As a result, the corrosion resistance is improved greatly. Copyright © 2015 John Wiley & Sons, Ltd.     

Effectiveness of 2‐mercaptobenzothiazole, 8‐hydroxyquinoline and benzotriazole as corrosion inhibitors on AA 2024‐T3 assessed by electrochemical methods

In this study, the effectiveness of 2‐mercaptobenzothiazole (2‐MBT), 8‐hydroxyquinoline and benzotriazole as corrosion inhibitors for AA 2024‐T3 aluminium alloy was evaluated. The corrosion behaviour in the presence of each compound was investigated by image‐assisted electrochemical noise analysis, electrochemical impedance spectroscopy, potentiodynamic polarization and the split cell technique. It was found that 2‐MBT has superior inhibition properties compared with the other inhibitors. In particular, the specimens immersed in 3.5% NaCl in the presence of 2‐MBT displayed high values of noise resistance that were maintained for over 400 h of testing, and high values of low‐frequency impedance, measured after immersion for 24 h. The split cell technique and potentiodynamic polarization tests indicated that only 2‐MBT decreases significantly both the anodic and the cathodic reaction rates. Scanning electron microscopy observations and energy dispersive X‐ray measurements complement the findings from electrochemical measurements indicating that only 2‐MBT protects the second phase particles, preventing dealloying, trenching and initiation of corrosion. © 2015 The Authors. Surface and Interface Analysis published by John Wiley & Sons Ltd.     

Formation of artificial micro‐pits on Al alloy with the photon rupture method and the localized corrosion behavior of the formed pits

An in situ artificial micro‐pit fabrication method with an area selective electrochemical measurement technique was applied to investigate the effect of the geometry of artificially formed pits on their localized corrosion behavior in anodized 1000 series aluminum. This technique enables the fabrication of artificial micro‐pits with different aspect ratios (pit depth/pit diameter) in solutions. The aspect ratios of the fabricated artificial micro‐pits in this experiment could be varied from 0.13 to 1.83 by controlling the irradiation time of the focused pulsed YAG laser beam. By applying a constant potential to the final laser‐beam‐irradiated spot in chloride environments, localized dissolution occurred only at the laser beam irradiated area, because the anodic oxide film acted as an insulator. The corrosion current and charge increase with increasing aspect ratio at any applied potential. Copyright © 2010 John Wiley & Sons, Ltd.     

Mechanical property and corrosion resistance of zirconia/polydopamine nanocomposite multilayer films fabricated via a novel non‐electrostatic layer‐by‐layer assembly technique

Zirconia/polydopamine (ZrO₂/PDA) nanocomposite multilayer films were constructed on Si substrate via a novel nonelectrostatic layer‐by‐layer (NELBL) assembly technique. The building block of this technique is the newly reported dopamine molecule, which can be attached to almost all material surfaces and undergo oxidation‐polymerization to form PDA layers; more importantly, the outer hydroxyl groups of the PDA layer can chelated with certain inorganic oxide nanoparticles to generate oxide films. Thus, ZrO₂/PDA nanocomposite multilayer films were fabricated by sequential NELBL deposition of PDA and ZrO₂ nanoparticles. The formation of the ZrO₂/PDA nanocomposite multilayer films was monitored by the water contact angle (WCA) and ellipsometric thickness measurements, while the microstructure of the fabricated films was analyzed by means of atomic force microscope (AFM), field emission scanning electron microscope (FESEM), X‐ray photoelectron spectrum (XPS), and X‐ray diffraction (XRD) analysis. The mechanical and anticorrosion behaviors of the annealed ZrO₂/PDA nanocomposite multilayers were found to be greatly enhanced as compared with that of the annealed homogeneous ZrO₂ film. The better mechanical and anticorrosion behaviors of the annealed ZrO₂/PDA nanocomposite multilayers than the annealed homogeneous ZrO₂ film may be closely related to their special microstructure. Namely, the organic–inorganic hybrid microstructure of the annealed ZrO₂/PDA nanocomposite multilayers may largely account for the increased nanohardness and corrosion resistance. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of formulation of silica‐based solution on corrosion resistance of silicate coating on hot‐dip galvanized steel

Several silica‐based solutions with 50 g/l of SiO₂ were prepared from sodium silicate solutions and silica sol; the silicate conversion coatings were obtained by immersing hot‐dip galvanized steel sheets in these solutions. These solutions were characterized using high‐resolution transmission electron microscopy and ²⁹Si nuclear magnetic resonance; the morphology of the coatings was observed by SEM and atomic force microscopy while the corrosion resistance was evaluated by electrochemical measurements as well as neutral salt spray tests. The results show that the coatings obtained from the single silica sol solution had poor adhesion and the coating obtained from the sodium silicate solution with low SiO₂/Na₂O molar ratio was uneven. By adding the silica sol to the silicate solution with low molar ratio, uniform coatings with better protection property were obtained. According to the results of ²⁹Si nuclear magnetic resonance spectra, the effects of the distribution of silicate anions with various polymerization degrees in the silica‐based solutions on the microstructure and corrosion resistance of the silicate coatings are discussed. Copyright © 2016 John Wiley & Sons, Ltd.     

Dispersive micro‐solid‐phase extraction of benzoylurea insecticides in honey samples with a β‐cyclodextrin‐modified attapulgite composite as sorbent

A β‐cyclodextrin‐modified attapulgite composite was prepared and used as a dispersive micro‐solid‐phase extraction sorbent for the determination of benzoylurea insecticides in honey samples. Parameters that may influence the extraction efficiency, such as the type and volume of the eluent, the amount of the sorbent, the extraction time and the ionic strength were investigated and optimized using batch and column procedures. Under optimized conditions, good linearity was obtained for all of the tested compounds, with R² values of at least 0.9834. The limits of detection were determined in the range of 0.2–1.0 μg/L. The recoveries of the four benzoylurea insecticides in vitex honey and acacia honey increased from 15.2 to 81.4% and from 14.2 to 82.0%, respectively. Although the β‐cyclodextrin‐modified attapulgite composite did not show a brilliant adsorption capacity for the selected benzoylurea insecticides, it exhibited a higher adsorption capacity toward relatively hydrophobic compounds, such as chlorfluazuron and hexaflumuron (recoveries in vitex honey samples ranged from 70.0 to 81.4% with a precision of 1.0–3.7%). It seemed that the logP_ow of the benzoylurea insecticides is related to their recoveries. The results confirmed the possibility of using cyclodextrin‐modified palygorskite in the determination of relatively hydrophobic trace pharmaceutical residues.     

Effect of nano‐modified SiO2/Al2O3 mixed‐matrix micro‐composite fillers on thermal,mechanical, and tribological properties of epoxy polymers

Thermo‐mechanically durable industrial polymer nanocomposites have great demand as structural components. In this work, highly competent filler design is processed via nano‐modified of micronic SiO₂/Al₂O₃ particulate ceramics and studied its influence on the rheology, glass transition temperature, composite microstructure, thermal conductivity, mechanical strength, micro hardness, and tribology properties. Composites were fabricated with different proportions of nano‐modified micro‐composite fillers in epoxy matrix at as much possible filler loadings. Results revealed that nano‐modified SiO₂/Al₂O₃ micro‐composite fillers enhanced inter‐particle network and offer benefits like homogeneous microstructures and increased thermal conductivity. Epoxy composites attained thermal conductivity of 0.8 W/mK at 46% filler loading. Mechanical strength and bulk hardness were reached to higher values on the incorporation of nano‐modified fillers. Tribology study revealed an increased specific wear rate and decreased friction coefficient in such fillers. The study is significant in a way that the design of nano‐modified mixed‐matrix micro‐composite fillers are effective where a high loading is much easier, which is critical for achieving desired thermal and mechanical properties for any engineering applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Surface modification of titanium by using plasma‐induced graft‐polymerization

Plasma‐induced graft‐polymerization (PIGP) method was utilized in this study to improve corrosion behavior and biocompatibility of titanium (Ti) surface. Bioactive molecule polyacrylamide (PAM) was immobilized onto Ti surface by introducing silanederivatized spacer arms as an intermediary for the covalent linkage. Ti was firstly activated by O₂ plasma, and oxygen‐containing groups were introduced on its surface consequently. The intermediary mercapto silane spacer molecules were then covalently linked to the oxidated surface, followed by the covalent binding of PAM and the sulfhydryl‐terminal groups via PIGP. Surface analyses following modification process included water contact angles (CA), SEM, attenuated total reflection‐Fourier transform infrared spectroscopy (ATR‐FTIR), XPS and atomic force microscope (AFM). The results revealed the effectiveness of this method on immobilizing PAM to Ti surface, and the hydrophilicity of modified surface improved remarkably. In addition, potentiodynamic polarization and cellular proliferation tests were implemented to validate the enhanced corrosion‐resistance and biocompatibility of modified Ti surface, respectively. Copyright © 2011 John Wiley & Sons, Ltd.     

Dispersive micro‐solid‐phase extraction using carbon‐based adsorbents for the sensitive determination of verapamil in plasma samples coupled with capillary electrophoresis

A dispersive micro‐solid‐phase extraction procedure coupled with capillary electrophoresis ultraviolet detection was developed for determination of verapamil in plasma samples. Graphene oxide/polydopamin was synthesized by a one‐step polymerization method, and graphene oxide/Fe₃O₄ (magnetic graphene oxide) nanocomposite was prepared by coprecipitation method. Moreover, they were fully characterized. The use of hazardous and water‐immiscible solvents was scaled down, and only 500 μL of acetone was required as the desorption solvent. The detector response concentration plots were linear in the range of 5–500 ng/mL, and the proposed method was validated according to guidelines. The precision and accuracy were less than 15%. Dispersive micro‐solid‐phase extraction method provides a rapid, environmentally friendly, and sensitive analysis for the verapamil in patient plasma samples, which is adequate for therapeutic drug monitoring and pharmacokinetic studies.     

Simultaneous determination of triclosan,triclocarban, and transformation products of triclocarban in aqueous samples using solid‐phase micro‐extraction‐HPLC‐MS/MS

The presence of triclosan and triclocarban, two endocrine‐disrupting chemicals and antimicrobial agents, and transformation products of triclocarban, 1,3‐di(phenyl)urea, 1,3‐bis(4‐chlorophenyl)urea and 1,3‐bis(3,4‐dichlorophenyl)urea, in tap water, treated household drinking water, bottled water, and river water samples were investigated using solid‐phase micro‐extraction coupled with‐HPLC‐MS/MS, a rapid, green, and sensitive method. Factors influencing the quantity of the analytes extracted onto the solid‐phase micro‐extraction fiber, such as addition of salt, sample pH, extraction time, desorption time, and sample volume, were optimized using solid‐phase micro‐extraction‐HPLC‐MS/MS. The results showed that the method gave satisfactory sensitivities and precisions for analyzing sub‐part‐per‐trillion levels of triclosan, triclocarban, and transformation products of triclocarban in samples collected locally. The recoveries of analytes ranged from 97 to 107% for deionized water samples, and 99 to 110% for river water samples, and limits of detection were in the range of 0.32–3.44 and 0.38–4.67 ng/L for deionized water and river water samples, respectively. On average, the daily consumption of triclosan and triclocarban by an adult by consuming 2 liters of different types of drinking water were estimated to be in the range of 6.13–425 ng/day as a result of the concentrations of triclosan and triclocarban measured in this study.     

Morphological comparison of isotactic polypropylene parts prepared by micro‐injection molding and conventional injection molding

The morphological feature of microparts evolved during micro‐injection molding may differ from that of the macroparts prepared by conventional injection molding, resulting in specific physical properties. In this study, isotactic polypropylene (iPP) microparts with 200 µm thickness and macroparts with 2000 µm thickness were prepared, and their morphological comparison was investigated by means of polarized light microscopy (PLM), scanning electron microscopy (SEM), differential scanning calorimeter (DSC), and wide‐angle X‐ray diffraction (WAXD). The results presented some similarities and differences. PLM observations showed that the through‐the thickness‐morphology of micropart exhibited a similar “skin–core” structure as macropart, but presented a large fraction of shear layer in comparison to the macropart which presented a large fraction of core layer. The SEM observation of shear layer of micropart featured highly oriented shish‐kebab structure. The micropart had a more homogeneous distribution of lamellae thickness. The degree of crystallinity of the micropart was found to be higher than that of the macropart. High content of β‐crystal was found in micropart. The 2D WAXD pattern of the core layer of macropart showed full Debye rings indicating a random orientation, while the arcing of the shear layer indicates a pronounced orientation. The most pronounced arcing of the micropart indicates the most pronounced orientation of iPP chains within lamellae. Copyright © 2011 John Wiley & Sons, Ltd.     

Application of carbon nanotubes modified with a Keggin polyoxometalate as a new sorbent for the hollow‐fiber micro‐solid‐phase extraction of trace naproxen in hair samples with fluorescence spectrophotometry using factorial experimental design

A sensitive technique to determinate naproxen in hair samples was developed using hollow‐fiber micro‐solid‐phase combined with fluorescence spectrophotometry. The incorporation of multi‐walled carbon nanotubes modified with a Keggin polyoxometalate into a silica matrix prepared by the sol–gel method was reported. In this research, the Keggin carbon nanotubes /silica composite was used in the pores and lumen of a hollow fiber as the hollow‐fiber micro‐solid‐phase extraction device. The device was used for the microextraction of the analyte from hair and water samples under the optimized conditions. An orthogonal array experimental design with an OA24 (4⁶) matrix was employed to optimize the conditions. The effect of six factors influencing the extraction efficiency was investigated: pH, salt, volume of donor and desorption phase, extraction and desorption time. The effect of each factor was estimated using individual contributions as response functions in the screening process. Analysis of variance was employed for estimating the main significant factors and their contributions in the extraction. Calibration curve plot displayed linearity over a range of 0.2–10 ng/mL with detection limits of 0.072 and 0.08 ng/mL for hair and aqueous samples, respectively. The relative recoveries in the hair and aqueous matrices ranged from 103–95%. The relative standard deviation for fiber‐to‐fiber repeatability was 3.9%.     

Mechanical polishing,surface roughness,near‐surface deformation,and electrochemical corrosion of Alloy 690TT

The effects of mechanical grinding/polishing, surface roughness, and near‐surface deformation on the electrochemical corrosion behavior of thermally treated (TT) Alloy 690 were studied in a sodium chloride solution. The X‐ray photoelectron spectroscopy and transmission electron microscopy analyses revealed that mechanical grinding/polishing can change the ratio of the elements at the surface of the as‐received Alloy 690TT specimen by removing its Cr‐rich outer layer and causing deformation at the near‐surface microstructure, something which has a direct impact on the rate of the oxygen reduction reaction (ORR), the pitting potential (E_pit), and the corrosion potential (E_corr) of Alloy 690TT. It was observed that the ratio of Cr in the surface is a significant factor that controls the rate of the ORR and the corrosion parameters such as E_corr. Higher amounts of Cr at the surface accelerate the ORR. The near‐surface deformation shifts the E_pit values towards less positive potentials. It was also found that due to the different near‐surface chemical composition of the as‐received Alloy 690TT specimen compared with the ground and the polished specimens, the surface roughness parameters do not have a regular correlation with the rate of the ORR and the values of the E_corr and the E_pit. Only the passive current density increases when the surface roughness is increased. Copyright © 2015 John Wiley & Sons, Ltd.     

Determination of chloramphenicol in biological matrices by solid‐phase membrane micro‐tip extraction and capillary electrophoresis

Solid‐phase membrane micro‐tip extraction (SPMMTE) and capillary electrophoresis (CE) methods were developed and validated for analysis of chloramphenicol in human plasma and urine samples. Iron composite nanoparticles were prepared using green technology. CE was carried out using a silica capillary (60 cm × 50 μm i.d.), phosphate buffer (50 mm , 8.0 pH)–acetonitrile (95:5, v/v) as the background electrolyte, 10 kV voltage, 280 nm detection, 20 s injection time and 27 ± 1°C temperature. Frusemide was used as an internal standard. The values of migration time, electrophoretic mobility, electrophoretic velocity and theoretical plates of chloramphenicol were 12.254 min, 4.44 × 10, 7.41 × 10 and 11,227. The limits of detection and quantitation of chloramphenicol were 0.1 and 1.0 μg/mL. Recovery of chloramphenicol in the standard solution was 95%. Solid‐phase membrane micro‐tip extraction and capillary electrophoresis methods may be used to analyze chloramphenicol in human plasma and urine samples of any patient.     

Dispersive micro‐solid‐phase extraction combined with online preconcentration by capillary electrophoresis for the determination of glycopyrrolate stereoisomers in rat plasma

A simple and sensitive analytical method for four isomers of glycopyrrolate in rat plasma was developed using cation‐selective exhaustive injection‐sweeping cyclodextrin‐modified electrokinetic chromatography (CSEI‐Sweeping‐CDEKC) for online enrichment combined with dispersive micro‐solid‐phase extraction pretreatment. The CSEI‐Sweeping‐CDEKC was conducted on an uncoated fused silica capillary (40.2 cm × 75 μm) with an applied voltage of –20 kV. The electrophoretic analysis was carried out in 30 mM phosphate solution at pH 2.0 containing 20 mg/mL sulfated‐β‐cyclodextrin and 5% acetonitrile. Under these optimized conditions, the detection limit for racemic glycopyrrolate was found to be 2.0 ng/mL and this method could increase 495‐fold detection sensitivity compared with the traditional injection method. Additionally, the parameters that affected the extraction efficiency of dispersive micro‐solid‐phase extraction were also examined systematically. The glycopyrrolate isomers in rat plasma samples as low as 0.0625 μg/mL were able to be separated and detected by capillary electrophoresis with the aid of CSEI‐sweeping. The findings of this study show that the dispersive micro‐solid‐phase extraction pretreatment coupled with CSEI‐Sweeping‐CDEKC is a rapid and convenient method for analyzing glycopyrrolate isomers in rat plasma.     

Cross‐linked waterborne alkyd hybrid resin coatings modified by fluorinated acrylate‐siloxane with high waterproof and anticorrosive performance

Waterborne alkyd resin coatings are ideal for use as corrosion protection coatings because of its high cost‐effective and environmental advantages. However, their uses are restricted to general applications due to their poor acid, water, and alkali resistance. In this work, waterborne alkyd hybrid resins modified with fluorinated acrylate‐siloxane were synthesized via a surfactant‐free miniemulsion polymerization process using maleic anhydride and silicon modified alkyd resin, dodecafluoroheptyl methacrylate, methyl methacrylate, and butyl acrylate as monomers. And then, crosslinking alkyd resin films were prepared at room temperature using trimethylolpropane‐tris‐(β‐N‐azir‐idinyl) propionate (XR‐100) as the crosslinking agent. The acquired films had lower water absorption and higher water contact angles and had better mechanical/thermal properties, as well as good waterproof property. Most importantly, the electrochemical corrosion studies revealed that the cross‐linked coating exhibited superior corrosion resistance performance with an inhibition efficiency of 99.95% and a corrosion rate of 6.95 × 10^?3 mm per year.     

A rapid MCM‐41 dispersive micro‐solid phase extraction coupled with LC/MS/MS for quantification of ketoconazole and voriconazole in biological fluids

A rapid dispersive micro‐solid phase extraction (D‐μ‐SPE) combined with LC/MS/MS method was developed and validated for the determination of ketoconazole and voriconazole in human urine and plasma samples. Synthesized mesoporous silica MCM‐41 was used as sorbent in d ‐μ‐SPE of the azole compounds from biological fluids. Important D‐μ‐SPE parameters, namely type desorption solvent, extraction time, sample pH, salt addition, desorption time, amount of sorbent and sample volume were optimized. Liquid chromatographic separations were carried out on a Zorbax SB‐C₁₈ column (2.1 × 100 mm, 3.5 μm), using a mobile phase of acetonitrile–0.05% formic acid in 5 mm ammonium acetate buffer (70:30, v /v). A triple quadrupole mass spectrometer with positive ionization mode was used for the determination of target analytes. Under the optimized conditions, the calibration curves showed good linearity in the range of 0.1–10,000 μg/L with satisfactory limit of detection (≤0.06 μg/L) and limit of quantitation (≤0.3 μg/L). The proposed method also showed acceptable intra‐ and inter‐day precisions for ketoconazole and voriconazole from urine and human plasma with RSD ≤16.5% and good relative recoveries in the range 84.3–114.8%. The MCM‐41‐D‐μ‐SPE method proved to be rapid and simple and requires a small volume of organic solvent (200 μL); thus it is advantageous for routine drug analysis.