MoO2 nanosheets anchored with Co nanoparticles as a bifunctional electrocatalytic platform for overall water splitting.

Electrochemical water splitting is one of the potential commercial techniques to produce clean hydrogen energy because of the high efficiency and environmental friendliness. However, development of low-cost bifunctional electrocatalysts that can replace Pt-based catalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is challenging. Herein, Co nanoparticles (NPs) are anchored on MoO2 nanosheets (Co/MoO2) by thermal reduction of the CoMoO4 nanosheet array in Ar/H2. The uniformly distributed Co NPs improve the electron transfer capability and modulate the surface states of the MoO2 nanosheets to enhance hydrogen desorption and HER kinetics. Moreover, the Co/MoO2 composite is beneficial to the interfacial structure and the MoO2 nanosheets prevent aggregation of Co NPs to improve the intrinsic OER characteristics in the alkaline electrolyte. As a result, the Co/MoO2 electrocatalyst shows low HER and OER overpotentials of 178 and 318 mV at a current density of 10 mA cm-2 in 1 M KOH. The electrolytic cell consisting of the bifunctional Co/MoO2 electrodes shows a small voltage of 1.72 V for a current density of 10 mA cm-2 in overall water splitting.

Development, retainment, and assessment of the graphite-electrolyte interphase in Li-ion batteries regarding the functionality of SEI-forming additives.

Formation of a decent solid-electrolyte interphase (SEI) is recognized as an approach to improve the performance of lithium-ion batteries. SEI is a passivation layer generated on the anode during the initial cycles. Characteristics of the graphite SEI depend on the operational parameters, state of the anode, and the content of the electrolyte. Introducing reduction-type additives to the carbonate electrolytes has been one of the most practiced methods to generate an effective SEI on carbonous anodes. To track the role of additives in SEI evolution, first, we have presented a general review on what is currently understood about the SEI formation processes and the impacting parameters. In the second step, the most reported methods to study and analyze the functionality of the SEI-forming additives are classified. As the third part, different reduction-type additives are categorized, and their performances are comparatively reviewed.

Novel proton conducting core-shell PAMPS-PVBS@Fe2TiO5 nanoparticles as a reinforcement for SPEEK based membranes.

In this study, new nanocomposite membranes from sulfonated poly (ether ether ketone) (SPEEK) and proton-conducting Fe2TiO5 nanoparticles are prepared by the solution casting method. Sulfonated core-shell Fe2TiO5 nanoparticles are synthesized by redox polymerization. Therefore, 4-Vinyl benzene sulfonate (VBS) and 2-acrylamide-2-methyl-1-propane sulfonic acid (AMPS) are grafted on the surface of nanoparticles through radical polymerization. The different amounts of hybrid nanoparticles (PAMPS@Fe2TiO5 and PVBS@Fe2TiO5) are incorporated into the SPEEK matrix. The results show higher proton conductivity for all prepared nanocomposites than that of the SPEEK membrane. Embedding the sulfonated Fe2TiO5 nanoparticles into the SPEEK membrane improves proton conductivity by creating the new proton conducting sites. Besides, the nanocomposite membranes showed improved mechanical and dimensional stability in comparison with that of the SPEEK membrane. Also, the membranes including 2 wt% of PAMPS@Fe2TiO5 and PVBS@Fe2TiO5 nanoparticles indicate the maximum power density of 247 mW cm-2 and 226 mW cm-2 at 80 °C, respectively, which is higher than that of for the pristine membrane. Our prepared membranes have the potential for application in polymer electrolyte fuel cells.

Fabrication and performance evaluation of new nanocomposite membranes based on sulfonated poly(phthalazinone ether ketone) for PEM fuel cells.

The purpose of this work is to enhance the proton conductivity and fuel cell performance of sulfonated poly(phthalazinone ether ketone) (SPPEK) as a proton exchange membrane through the application of SrTiO3 perovskite nanoparticles. Nanocomposite membranes based on SPPEK and SrTiO3 perovskite nanoparticles were prepared via a casting method. The highest proton conductivity of nanocomposite membranes obtained was 120 mS cm-1 at 90 °C and 95% RH. These enhancements could be related to the hygroscopic structure of SrTiO3 perovskite nanoparticles and the formation of hydrogen bonds between nanoparticles and water molecules. The satisfactory power density, 0.41 W cm-2 at 0.5 V and 85 °C, of the nanocomposite membrane (5 wt% content of nanoparticles) confirms their potential for application in the PEM fuel cells.

Controllable Pulse Reverse Electrodeposition of Mesoporous Li xMnO2 Nano/Microstructures with Enhanced Electrochemical Performance for Li-Ion Storage.

Given the ever-growing demand of electric vehicles and renewable energies, addressing the poor cyclic stability of lithium manganese dioxide is an urgent challenge. In this study, pulse reverse current as the driving force of a one-pot anodic electrodeposition was exploited to design the physicochemical and electrochemical characteristics of lithium manganese dioxides as cathode materials of Li-ion battery. The pulse reverse parameters, including the span of anodic and cathodic current application ( ta and tc) and frequency ( f'), were systematically modulated to determine the optimized values through monitoring the physicochemical properties using X-ray diffraction, thermogravimetric analysis/differential scanning calorimetry, field emission scanning electron microscopy, transmission electron microscopy, energy-dispersive spectrometry, Raman spectroscopy, N2 adsorption-desorption isotherms, and inductively coupled plasma-optical emission spectroscopy, as well as the electrochemical properties using cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge at different currents. Based on the results, Li0.65MnO2 synthesized using ta = 95 ms, tc = 5 ms, and f' = 8.33 Hz at the constant magnitude of anodic peak current density of 1 mA dm-2 was determined as the optimized sample. The optimized lithium manganese dioxide rendered superior electrochemical performance with the initial discharge capacity of 283 mAh g-1, which accounts for 96.4% of the theoretical discharge capacity, preserving 88.3% of this capacity after 300 cycles at 0.1 C and, in the meantime, was able to release a discharge capacity of 115 mAh g-1 even after cycling at a higher current of 10 C. The superior electrochemical behavior of Li0.65MnO2 was attributed to the exclusive hierarchical urchin-like morphology as well as mesoporous nano/microstructures having a notably high Brunauer-Emmett-Teller surface area of 320.12 m2 g-1 alongside mixed-phase α/γ structure owing to the larger 2 × 2 tunnels, which offer more facile Li+ diffusion.

Optimization of effective parameters in the synthesis of nanopore anodic aluminum oxide membrane and arsenic removal by prepared magnetic iron oxide nanoparicles in anodic aluminum oxide membrane via ultrasonic-hydrothermal method.

In this study, a new anodized aluminum oxide (AAO) nanostructure membrane was synthesized by anodization process under a constant voltage, in oxalic acid solution that was improved with trace amounts of sulfuric acid at room temperature. The effect of various parameters on the morphology of the synthesized nanostructures such as voltage, electrolyte composition, anodization time and type of stripping solution were investigated. According to the results, corrosion of the walls, size regularity, diameter and number of the pores increased in the presence of sulfuric acid (0.018 mol.L-1). Nitrogen adsorption-desorption analysis confirmed significant porosity, array and uniformity of the pore size in the synthesized nanoporous membrane. A new modification method was used based on ultrasonic-hydrothermal method to modify the synthesized AAO with Fe3O4/SiO2 nanoparticles for metals and metalloids removal from aqueous solution. In this method, Fe3O4/SiO2 nanoparticles were placed very regularly and uniformly on the surface and inside the pores. This modification was confirmed by characterization techniques. The modified AAO@Fe3O4/SiO2 membrane showed excellent results for removing arsenic from aqueous media.

The Combination Process for Preparative Separation and Purification of Paclitaxel and 10-Deacetylbaccatin III Using Diaion® Hp-20 Followed by Hydrophilic Interaction Based Solid Phase Extraction.

There is no other naturally occurring defense agent against cancer that has a stronger effect than paclitaxel, commonly known under the brand name of Taxol®. The major drawback for the more widespread use of paclitaxel and its precious precursor, 10-deacetylbaccatin III (10-DAB III), is that they require large-scale extraction from different parts of yew trees (Taxus species), cell cultures, taxane-producing endophytic fungi, and Corylus species. In our previous work, a novel online two-dimensional heart-cut liquid chromatography process using hydrophilic interaction/ reversed-phase chromatography was used to introduce a semi-preparative treatment for the separation of polar (10-deacetylbaccatin III) and non-polar (paclitaxel) taxanes from Taxus baccata L. In this work, a combination of the absorbent (Diaion® HP-20) and a silica based solid phase extraction is utilized as a new, efficient, and cost effective method for large-scale production of taxanes. This process avoids the technical problem of two-dimensional preparative liquid chromatography. The first stage of the process involves discarding co-extractive polar compounds including chlorophylls and pigments using a non-polar synthetic hydrophobic absorbent, Diaion® HP-20. Extract was then loaded on to a silica based hydrophilic interaction solid phase extraction (silica 40-60 micron). Taxanes was eluted using a mixture of water and methanol at the optimized ratio of 70:30. Finally, the fraction containing taxanes was applied to semi-preparative reversed phase HPLC. The results revealed that using this procedure, paclitaxel and 10-DAB III could be obtained at 8 and 3 times more, respectively than by the traditional method of extraction.

Paclitaxel molecularly imprinted polymer-PEG-folate nanoparticles for targeting anticancer delivery: Characterization and cellular cytotoxicity.

The aim of this work was to synthesize molecularly imprinted polymer-poly ethylene glycol-folic acid (MIP-PEG-FA) nanoparticles for use as a controlled release carrier for targeting delivery of paclitaxel (PTX) to cancer cells. MIP nanoparticles were synthesized by a mini-emulsion polymerization technique and then PEG-FA was conjugated to the surface of nanoparticles. Nanoparticles showed high drug loading and encapsulation efficiency, 15.6 ± 0.8 and 100%, respectively. The imprinting efficiency of MIPs was evaluated by binding experiments in human serum. Good selective binding and recognition were found in MIP nanoparticles. In vitro drug release studies showed that MIP-PEG-FA have a controlled release of PTX, because of the presence of imprinted sites in the polymeric structure, which makes it is suitable for sustained drug delivery. The drug release from polymeric nanoparticles was indeed higher at acidic pH. The molecular structure of MIP-PEG-FA was confirmed by Hydrogen-Nuclear Magnetic Resonance (H NMR), Fourier Transform InfraRed (FT-IR), and Attenuated Total Reflection (ATR) spectroscopy, and their thermal behaviors by Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA). Scanning Electron Microscopy (SEM) and Photon Correlation Spectroscopy (PCS) results showed that nanoparticles have a smooth surface and spherical shape with an average size of 181 nm. MIP-PEG-FA nanoparticles showed a greater amount of intracellular uptake in folate receptor-positive cancer cells (MDA-MB-231 cells) in comparison with the non-folate nanoparticles and free PTX, with half maximal inhibitory concentrations (IC50) of 4.9 ± 0.9, 7.4 ± 0.5 and 32.8 ± 3.8 nM, respectively. These results suggest that MIP-PEG-FA nanoparticles could be a potentially useful drug carrier for targeting drug delivery to cancer cells.

Surface modification of Fe2TiO5 nanoparticles by silane coupling agent: Synthesis and application in proton exchange composite membranes.

Modifying surfaces of nanoparticles with silane coupling agent provides a simple method to alter their surface properties and improve their dispersibility in organic solvents and polymer matrix. Fe2TiO5 nanoparticles (IT) were modified with 3-aminopropyltriethoxysilane (APTES) as novel reinforcing filler for proton exchange membranes. The main operating parameters such as reaction time (R.T), APTES/IT and triethylamine (TEA)/IT ratios have been optimized for maximum grafting efficiency. The optimum conditions for R.T, APTES/IT and TEA/IT ratios were 6h, 4 and 0.3 respectively. It was observed that the APTES/IT and TEA/IT ratios were the most significant parameters affecting the grafting percentage. Modified nanoparticles were characterized using FT-IR, TGA, SEM, TEM and XRD techniques. Effects of modified nanoparticles in proton exchange membrane fuel cells (PEMFC) were evaluated. The resulting nanocomposite membranes exhibited higher proton conductivity in comparison with pristine SPPEK and SPPEK/IT membranes. This increase is attributed to connectivity of the water channels which creates more direct pathways for proton transport. Composite membrane with 3% AIT (6.46% grafting amount) showed 0.024 S cm(-1) proton conductivity at 25 °C and 149 mW cm(-2) power density (at 0.5V) at 80 °C which were about 243% and 51%, respectively higher than that of pure SPPEK.

N-butylamine functionalized graphene oxide for detection of iron(III) by photoluminescence quenching.

An N-butylamine functionalized graphene oxide nanolayer was synthesized and characterized by ultraviolet (UV)-visible spectrometry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. Detection of iron(III) based on photoluminescence spectroscopy was investigated. The N-butylamine functionalized graphene oxide was shown to specifically interact with iron (III), compared with other cationic trace elements including potassium (I), sodium (I), calcium (II), chromium (III), zinc (II), cobalt (II), copper (II), magnesium (II), manganese (II), and molybdenum (VI). The quenching effect of iron (III) on the luminescence emission of N-butylamine functionalized graphene oxide layer was used to detect iron (III). The limit of detection (2.8 × 10(-6) M) and limit of quantitation (2.9 × 10(-5) M) were obtained under optimal conditions.

Three-phase molecularly imprinted sol-gel based hollow fiber liquid-phase microextraction combined with liquid chromatography-tandem mass spectrometry for enrichment and selective determination of a tentative lung cancer biomarker.

In the present study, the modification of a polysulfone hollow fiber membrane with in situ molecularly imprinted sol-gel process (as a novel and one-step method) was prepared and investigated. 3-(propylmethacrylate)trimethoxysilane (3PMTMOS) as an inorganic precursor was used for preparation of molecularly imprinted sol-gel. The modified molecularly imprinted sol-gel hollow fiber membrane (MSHM) was used for the liquid-phase microextraction (LPME) of hippuric acid (HA) in human plasma and urine samples. MSHM as a selective, robust, and durable tool was used for at least 50 extractions without significant decrease in the extraction efficiency. The non-molecularly imprinted sol-gel hollow fiber membrane (NSHM) as blank hollow fiber membrane was prepared by the same process, only without HA. To achieve the best condition, influential parameters on the extraction efficiency were thoroughly investigated. The capability of this robust, green, and simple method for extraction of HA was successfully accomplished with LC/MS/MS. The limits of detection (LOD) and quantification (LOQ) in human plasma and urine samples were 0.3 and 1.0nmolL(-1), respectively. The standard calibration curves were obtained within the concentration range 1-2000nmolL(-1) for HA in human plasma and urine. The coefficients of determination (r(2)) were ≥0.998. The obtained data exhibited recoveries were higher than 89% for the extraction of HA in human plasma and urine samples.

A new strategy for surface modification of polysulfone membrane by in situ imprinted sol-gel method for the selective separation and screening of L-Tyrosine as a lung cancer biomarker.

In this work, a novel method based on in situ molecularly imprinted sol-gel for the surface modification of a polysulfone membrane (PSM) was developed. A modified molecularly imprinted sol-gel polysulfone membrane (MSM) was placed in a homemade plastic tube and coupled on-line with LC/MS/MS for the selective extraction and screening of l-Tyrosine (Tyr) as a tentative lung cancer biomarker in human plasma samples. The existence of molecularly imprinted sol-gel layers on both sides of a PSM was examined using scanning electron microscopy (SEM). To evaluate the role of precursor in the extraction performance, repeatability, and selectivity of developed method, three precursors, 3-(propylmethacrylate) trimethoxysilane (P1), 3-(triethoxysilyl)-propylamine (P2), tetraethyl orthosilicate (P3), individually and together were used for treatment of PSM. Our investigation showed that a single precursor's route is more repeatable, straightforward, precise, accurate, and selective for the extraction of Tyr in plasma samples. Moreover, to achieve the best conditions and extraction efficiency, the effect of influential parameters, including the conditioning, washing, and elution of solvents, sample flow rate, loading time, desorption time, loading sample volume, salt effect, pH, and adsorption capacity for the most efficiently prepared membranes were truly investigated. The non-molecularly imprinted sol-gel polysulfone membrane (NSM) was prepared as a blank via the same process but in the absence of the Tyr. The LOD (S/N = 3/1) was 0.1 nmol L(-1) and the LOQ (S/N = 10/1) was 0.34 nmol L(-1) for Tyr in the plasma samples. The linearity for the Tyr was in the range of 0.34-2000 nmol L(-1) in the plasma samples. The coefficients of determination values were ≥0.998 for all runs. The extraction recovery was between 80%-85% for Tyr in the plasma samples. In addition, MSM could be used for up to 50 extractions without a significant change in recovery percentage.

Fabrication of a novel electrospun molecularly imprinted nanomembrane coupled with high-performance liquid chromatography for the selective separation and determination of acesulfame.

A novel in situ molecularly imprinted sol-gel nanomembrane using nylon 6 as backbone was prepared by the electrospinning technique and coupled on-line with high-performance liquid chromatography. The prepared electrospun membrane exhibited extensive selectivity toward acesulfame in the presence of some selected sweeteners in a beverage sample, while the porosity and mechanical stability remained. The prepared electrospun membrane could be applied for 35 consequence extractions without a significant change in extraction recovery, swelling, and flooding. To achieve the best condition and efficiency for on-line extraction, the effect of influential parameters was investigated. The limit of detection (signal/noise = 3:1) and limit of quantification (signal/noise = 10:1) were 0.6 and 2.0 ng/mL for acesulfame in the beverage samples, respectively. The linearity for the acesulfame was in the range of 2.0-250 ng/mL in beverage samples. The coefficients of determination values were ≥0.997 for all runs. The extraction recoveries of acesulfame in the beverage samples were between 80 and 85%.

Molecularly imprinted sol-gel nanofibers based solid phase microextraction coupled on-line with high performance liquid chromatography for selective determination of acesulfame.

Sol-gel based molecularly imprinted polymer (MIP) nanofiber was successfully fabricated by electrospinning technique on the surface of a stainless steel bar. The manufactured tool was applied for on-line selective solid phase microextraction (SPME) and determination of acesulfame (ACF) as an artificial sweetener with high performance liquid chromatography (HPLC). The selective ability of method for the extraction of ACF was investigated in the presence of some selected sweeteners such as saccharine (SCH), aspartame (ASP) and caffeine (CAF). Electrospinning of MIP sol-gel solution on the stainless steel bar provided an unbreakable sorbent with high thermal, mechanical, and chemical stability. Moreover, application of the MIP-SPME tool revealed a unique approach for the selective microextraction of the analyte in beverage samples. In this work, 3-(triethoxysilyl)-propylamine (TMSPA) was chosen as a precursor due to its ability to imprint the analyte by hydrogen bonding, Van der Walls, and dipole-dipole interactions. Nylon 6 was also added as a backbone and support for the precursor in which sol could greatly growth during the sol-gel process and makes the solution electrospinable. Various effective parameters in the extraction efficiency of the MIP-SPME tool such as loading time, flow rate, desorption time, selectivity, and the sample volume were evaluated. The linearity for the ACF in beverage sample was in the range of 0.78-100.5 ng mL(-1). Limit of detection (LOD) and quantification (LOQ) were 0.23 and 0.78 ng mL(-1) respectively. The RSD values (n=5) were all below 3.5%at the 20 ng mL(-1) level.

On-line detection of hippuric acid by microextraction with a molecularly-imprinted polysulfone membrane sorbent and liquid chromatography-tandem mass spectrometry.

Destruction of sorbents during consecutive extractions using the micro-extraction by packed sorbent (MEPS) technique is a serious problem. In MEPS the complex matrix such as plasma and blood can affect the sorbent physical properties and the sorbent can be deteriorated after handling of few samples. To overcome this problem, the surface of a polysulfone membrane (PSM) was modified by a molecularly imprinted sol-gel and utilized for online extraction of a lung cancer biomarker, hippuric acid (HA), in biological matrices. The molecularly imprinted polymer membrane provided fast, sensitive, selective and robust sample preparation method for HA in biological fluids. In addition, MIP membrane could be used for up to 50 extractions without a significant change in extraction recovery. To achieve the best results, the parameters that influenced the extraction efficiency were thoroughly investigated. Moreover, for evaluating the performance of the molecularly imprinted sol-gel membrane (MISM), a non-molecularly imprinted sol-gel membrane (NISM) as a blank was prepared. The limits of detection (LOD) and quantification (LOQ) for HA in both plasma and urine samples were 0.30nmolL-1 and 1.0nmolL-1, respectively. Standard calibration curves were obtained over the range of 1-1000nmolL-1 for HA in plasma and urine samples. The coefficients of determination (R2) were ≥0.997. The extraction recoveries of HA from human plasma and urine samples were higher than 91%. The precision values for HA in plasma and urine samples were 2.2-4.8% and 1.1-6.7%, respectively.

Molecularly imprinted polymer cartridges coupled on-line with high performance liquid chromatography for simple and rapid analysis of human insulin in plasma and pharmaceutical formulations.

In this paper, a novel method is described for automated determination of human insulin in biological fluids using principle of sequential injection on a molecularly imprinted solid-phase extraction (MISPE) cartridge as a sample clean-up technique combined with high performance liquid chromatography (HPLC). The water-compatible molecularly imprinted polymers (MIPs) were prepared using methacrylic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linker, chloroform as a porogen and insulin as a template molecule. The imprinted polymers were then employed as the solid-phase extraction sorbent for on-line extraction of insulin from human plasma samples. To achieve the best condition, influential parameters on the extraction efficiency were thoroughly investigated. Rapid and simple analysis of the hormone was successfully accomplished through the good selectivity of the prepared sorbent coupled with HPLC. Limits of detection (LOD) and quantification (LOQ) of 0.2 ng mL(-1), 0.7 ng mL(-1), and 0.03 ng mL(-1), 0.1 ng mL(-1) were obtained in plasma and urine respectively. The obtained data exhibited the great recoveries for extraction of insulin from human plasma and pharmaceutical samples, higher than 87%.

Computational prediction and experimental selectivity coefficients for hydroxyzine and cetirizine molecularly imprinted polymer based potentiometric sensors.

In spite of the increasing usages number of molecularly imprinted polymers (MIPs) in many scientific applications, the theoretical aspects of participating intra molecular forces are not fully understood. This work investigates effects of the electrostatic force, the Mulliken charge and the role of cavity's backbone atoms on the selectivity of MIPs. Moreover, charge distribution, which is a computational parameter, was proposed for the prediction of the selectivity coefficients of MIP-based sensors. In the computational approaches and experimental study, methacrylic acid (MAA) was chosen as the functional monomer and ethylene glycol dimethacrylate (EGDMA) as the cross linker for hydroxyzine and cetirizine imprinted polymers. Ab initio, DFT B3LYP method was carried out on molecular optimization. With regard to results obtained from molecules optimization and hydrogen bonding properties, possible configurations of 1:n (n≤5) template/monomer complexes were designed and optimized. The binding energy for each complex in gas phase was calculated. Depending on the most stable configuration, hydroxyzine and cetirizine imprinted polymer models were designed. The calculations including the porogen were also investigated. The theoretical charge distributions for the template and some potential interfering molecules were calculated. The results showed a correlation between the selectivity coefficients and the theoretical charge distributions. The results surprisingly show that charge distribution based model was able to predict the selectivity coefficients of MIP based potentiometric sensors.

Molecularly imprinted solid-phase extraction for selective trace analysis of trifluoperazine.

In this study, a novel sample clean-up technique based on the molecularly imprinted solid-phase extraction procedure is described for the determination of trifluoperazine (TFP) in biological fluids. The water-compatible molecularly imprinted polymers (MIPs) were prepared by using methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross-linker, chloroform as porogen and TFP as the template molecule. The novel imprinted polymer was used as a solid-phase extraction sorbent for the extraction of TFP from human serum and urine samples. Various parameters affecting the extraction efficiency of the polymer were evaluated. The selectivity of MIPs was evaluated by checking several substances with molecular structures similar to the template. The limits of detection and quantification for TFP in urine samples were 0.06 and 0.2 µg/L, respectively. These limits for TFP in serum samples were 0.15 and 0.4 µg/L, respectively. The recovery values for serum and urine samples were higher than 92 and 93%, respectively.

Selective extraction of lamivudine in human serum and urine using molecularly imprinted polymer technique.

In this work, a novel technique is described for determination of lamivudine in biological fluids by molecularly imprinted polymers (MIPs) as the sample clean-up method joint with high performance liquid chromatography (HPLC). MIPs were prepared using methacrylic acid as functional monomer, ethylene glycol dimethacrylate as crosslinker, acetonitrile and tetrahydrofuran as porogen and lamivudine as the template molecule. The new imprinted polymer was used as a molecular sorbent for the separation of lamivudine from human serum and urine. Molecular recognition properties, binding capacity and selectivity of the MIPs were evaluated and the results showed that the obtained MIPs have a high affinity for lamivudine in aqueous medium. HPLC analyses showed that the extraction of lamivudine from serum and urine by MIPs had a linear calibration curve in the range of 60-700µg/L with excellent precisions of 2.73% for serum and 2.60% for urine. The limit of detection and quantization of lamivudine was 19.34 and 58.6µg/L in serum and 7.95 and 24.05µg/L in urine respectively. MIP extraction provided about 10 fold LOQ improvement in serum and 5 fold LOQ improvement in urine samples. The recoveries of lamivudine in serum and urine samples were found to be 84.2-93.5% and 82.5-90.8% respectively. Due to the high precision and accuracy, this method may be the UV-HPLC choice with MIP extraction for bioequivalence analysis of lamivudine in serum and urine.

On-line clean-up and determination of tramadol in human plasma and urine samples using molecularly imprinted monolithic column coupling with HPLC.

The applicability of an on-line solid phase extraction method using molecularly imprinted monolithic column was developed for the assay of tramadol (TRD) in urine and plasma samples. The monolithic column was prepared by using TRD as the template, methacrylic acid (MAA) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker and chloroform as the porogen with in situ molecular imprinting polymerization technique. Various parameters affecting the extraction efficiency of the monolithic column were evaluated. Chromatographic analysis of TRD after on-line clean-up of samples was performed by reversed-phase HPLC on an ACE column with ultraviolet detection at 218nm. The present work was successfully applied for automated simple analysis of TRD in urine and plasma samples with high recoveries between 90.5-93.1% and 93.3-96.0%, respectively. The results revealed that in concentration up to 500ng/mL of dextromethorphan (DEX), timolol (TMO) and O-desmethyltramadol (M1), the recoveries were not reduced more than 4.3% and 4.0% for plasma and urine samples, respectively. The limit of detection (S/N=3) and limit of quantification (S/N=10) for TRD in urine samples were 0.03ng/mL and 0.10ng/mL, and in plasma samples were 0.3 and 1.0ng/mL, respectively. Inter-column precision of the assays (n=3) for urine and plasma samples at the 100ng/mL TRD level were 4.0% and 4.2%, respectively.