GC Determination of Cisplatin in Serum and Urine of Cancer Patients after Chemotherapy as Platinum (II) Pyrrolidinedithiocarbamate Chelate

A gas chromatographic procedure has been developed for determination of cisplatin from pharmaceutical preparation, serum and urine after chemotherapy of cancer patients as platinum(II) pyrrolidinedithiocarbamate chelate. The elution was carried from the column DB-1701 (30 m × 0.32 mm i.d.) coupled with FID detection. Cu(II), Ni(II), Co(III), Mn(II), Fe(III), Zn(II) and VO(II) when present together with Pt(II) separated completely and did not affect the determination of platinum. The linear calibration curve for platinum (II) was within 1–30 μg mL^?1 with a detection limit of 300 ng mL^?1. The amount of cisplatin detected from serum and urine was 250–325 and 20–116 ng mL^?1 with relative standard deviations (RSD) of 0.8–1.2%, and 0.9–1.2%. The % recovery of Pt from serum and urine by standard addition was 98 and 98.2% with RSD 1.4 and 1.1%.     

Synthesis and application of a novel magnetic nanosorbent for determination of trace Cd(II), Ni(II), Pb(II), and Zn(II) in environmental samples

In this work for the first time, Fe₃O₄@SiO₂ core–shell nanoparticles functionalized with isatin groups as a magnetic nanosorbent was applied for the simultaneous extraction of trace amounts of cadmium(II), nickel(II), lead(II), and zinc(II). The characterization of this nanosorbent was studied using Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectrometry, X-ray diffraction, vibrating sample magnetometer and thermogravimetric analysis. The effect of several factors such as pH, amount of sorbent, extraction time, type and volume of the eluent, sample volume, sorption capacity, and potentially interfering ions was investigated. In the selected conditions, it was observed that the limits of detection were 0.11 ng mL^?1 for Cd(II), 0.28 ng mL^?1 for Ni(II), 0.47 ng mL^?1 for Pb(II), and 0.21 ng mL^?1 for Zn(II), and the maximum sorption capacity of this suggested magnetic nanosorbent was 120, 112, 100, and 100 mg g^?1 for Cd(II), Ni(II), Pb(II), and Zn(II), respectively. Also, the precision of the method (RSD%) for ten replicate measurements was found 2.5, 2.5, 2.8, and 3.1%, for Cd(II), Ni(II), Pb(II), and Zn(II) ions, respectively. Finally, the suggested procedure was applied for determination of cadmium(II), nickel(II), lead(II), and zinc(II) at trace levels in different water and agricultural products with satisfactory results.     

Application of Multivariate Calibration Methods for the Simultaneous Multiwavelength Spectrophotometric Determination of Fe(II), Cu(II), Zn(II), and Mn(II) in Mixtures

Abstract

A sensitive method for the simultaneous spectrophotometric determination of Fe(II), Cu(II), Zn(II), and Mn(II) in mixtures has been developed with the aid of multivariate calibration methods, such as classical least squares (CLS), principal component regression (PCR) and partial least squares (PLS). The method is based on the spectral differences of the analytes in their complexation reaction with 4‐(2‐pyridylazo)‐resorcinol (PAR) and the use of full spectra with wavelengths in the range of 300–600 nm. It was found that both the spectral positive and negative bands obtained against the PAR blank, are proportional to the concentration for each metal complex. The obtained linear calibration concentration ranges are 0.025–0.6, 0.05–0.8, 0.025–0.8, and 0.05–0.8 µg ml^?1 for Fe(II), Cu(II), Zn(II), and Mn(II), respectively, and the LODs for the four metal ions were found to be approximately 1–3×10^?2 µg ml^?1. The proposed method was applied to a verification set of synthetic mixtures of these four metal ions, with models built in three different wavelength ranges, i.e., 300–450, 450–600, and 300–600 nm, corresponding to the positive, negative bands and their combinations, respectively. It was shown that the PLS model for the 300–600 nm range gave the best results (RPE_T=6.9% and average recovery ～100%; cf. PCR: RPE_T=9.5% and average Recovery ～110%). This method was also successfully applied for the determination of the four metal ions in pharmaceutical preparations, chicken feedstuff, and water samples.     

Diphenyl diselenide grafted onto a Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>-chitosan composite as a new nanosorbent for separation of metal ions by effervescent salt-assisted dispersive magnetic micro solid-phase extraction

Diphenyl diselenide was immobilized on chitosan loaded with magnetite (Fe₃O₄) nanoparticles to give an efficient and cost-effective nanosorbent for the preconcentration of Pb(II), Cd(II), Ni(II) and Cu(II) ions by using effervescent salt-assisted dispersive magnetic micro solid-phase extraction (EA-DM-μSPE). The metal ions were desorbed from the sorbent with 3M nitric acid and then quantified via microflame AAS. The main parameters affecting the extraction were optimized using a one-at-a-time method. Under optimum condition, the limits of detection, linear dynamic ranges, and relative standard deviations (for n?=?3) are as following: Pb(II): 2.0 ng·mL^?1; 6.3–900 ng·mL^?1; 1.5%. Cd(II): 0.15 ng·mL^?1; 0.7–85 ng·mL^?1, 3.2%; Ni(II): 1.6 ng·mL^?1,.6.0–600. ng·mL^?1, 4.1%; Cu(II): 1.2 ng·mL^?1, 3.0–300 ng·mL^?1, 2.2%. The nanosorbent can be reused at least 4 times.

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Graphical abstract Fe₃O₄-chitosan composite was modified with diphenyl diselenide as a sorbent for separation of metal ions by effervescent salt-assisted dispersive magnetic micro solid-phase extraction.

     

Calix[4]pyrrole virtuous sensor: a selective and sensitive recognition for Pb(II) ions by spectroscopic and computational study

A novel supramolecular sensor derived from calix[4]pyrrole system i.e. calix[4]pyrrole bearing aminoanthraquinone derivative (CAAQ) have been designed and synthesized. The complexation behavior of metal cations [Ag(I), Ba(II), Ca(II), Ni(II), Co(II), Fe(III), Hg(II), Cu(II), Cr(II), Pb(II), Zn(II), (1 × 10^?4 M)] with CAAQ (1 × 10^?6 M) was studied by spectrophotometry and spectrofluorometry. Metal ion like Pb(II) produces red shift in absorption spectra and quenching in emission spectra likelihood of strong complexation of Pb(II) ions with CAAQ. Fluorescence cell imaging also supports the complexation of Pb(II) ions with CAAQ. The binding constants, quantum yield, stoichiometry of complex, mechanism of quenching by Stern–Volmer equation and Density functional theory calculation have been determined.     

FAAS determination of palladium after its selective recovery by silica modified with hydrazone derivative

Amino propyl silica (APS) gel reacts immediately with benzyl monopyridyl hydrazone (BMPH) to produce a new effective and selective derivative (BMPH-APS) for the separation and preconcentration of traces of Pd(II) in aqueous solution. Factors affecting the sorption and desorption of Pd ions have been investigated. Acidic aqueous solution of 0.5% thiourea in 0.5 mol L^?1 HCl has been used as eluent for the desorption of Pd(II). The stripped metal ion was determined by flame AAS. The modified silica quantitatively sorbed Pd(II) at pH 2–4 with a sorption capacity of 0.65 mmol g^?1 and preconcentration factor of 250 fold in less than one minute (t_1/2). Common other ions did not interfere except Co(II) which was eliminated by EDTA . The limit of detection (LOD) is 0.1 ng mL^?1 and the relative standard deviation (R. S. D.) for 10 replicate measurements at 20 ng mL^?1 Pd level was 1.51%. The method was successfully applied for Pd preconcentration in highly concentrated salt solutions and in spiked clay, road dust, scrap and water samples.     

Catalytic Square-Wave Voltammetric Determination of Acrylamide in Potato Chips

Abstract

Square-wave voltammetry is a fast technique used for determination of trace amounts of acrylamide. When cobalt(II) ions were added to the acrylamide solution, a catalytic peak at about ?1.35 V vs. Ag/AgCl was observed, which was proportional to acrylamide concentration. The calibration curve showed good linearity in the range of 200–800 ng mL^?1 of acrylamide with a regression coefficient of 0.9989. The limit of detection of the method was 3.52 ng mL^?1, and the relative standard deviations for concentrations of 300 ng mL^?1 and 700 ng mL^?1 were 99.8% × 10^?2 and 79.7% × 10^?2, respectively.     

Synthesis of a New Cu(II)-Ion Imprinted Polymer for Solid Phase Extraction and Preconcentration of Cu(II)

A new Cu(II)-ion imprinted polymer (IIP) has been synthesized by copolymerizing salicylic acid and formaldehyde as a monomer and crosslinker, respectively in the presence of Cu(II)-4-(2-pyridylazo) resorcinol complex. The imprinted Cu(II) ions were completely removed by leaching the IIP with 0.05 M EDTA. The maximum adsorption capacity for Cu(II) ions was 310 μg g^?1 at pH 6. The IIP was repeatedly used in adsorption–desorption experiments for seven times with recoveries ~95%. The relative selectivity factor (α _r) values of Cu(II)/Zn(II), Cu(II)/Cd(II), Cu(II)/Ni(II) and Cu(II)/Co(II) are 3.17, 2.90, 2.47 and 3.37, respectively. The detection limit corresponding to three times the standard deviation of the blank was found to be 3.0 μg L^?1. The developed IIP has also been tested for preconcentration and recovery of Cu(II) ions from water samples.     

Kinetics study of selective removal of lead(II) in an aqueous solution containing lead(II), copper(II) and cadmium(II) across bulk liquid membrane

Transport of Pb(II) ion from equimolar aqueous solutions of Pb(II), Cu(II) and Cd(II) as well as from aqueous solutions containing only Pb(II) source phase (C_metal = 1.0 × 10^?4 mol L^?1) through bulk liquid membranes containing crown ether and oleic acid as carrier has been investigated. The initial fluxes of transported metal ions depend on the hydrophile–lipophile balance (HLB) and molar volumes (Vx) of crown ethers. The initial fluxes of Pb(II), Cu(II), and Cd(II) decrease with increase of HLB value for azacrown ether, i.e., tetraaza-14-crown-4 (A₄14C4), L1 > benzo-15-crown-5 (B15C5), L2 > 4′-Aminobenzo-15C5, L3 > nitrobenzo-15-crown-5 (NB15C5), L4. The selectivity of the metal ions showed the following separation factors (SF): SF_Pb–Cu = 2.15, SF_Cu–Cd = 2.10, SF_Pb–Cd = 4.52. The highest transport recovery for Pb(II) was observed for L1 (99.3 %).     

Flame atomic absorption spectrometric determination of Cd(II), Ni(II), Co(II) and Cu(II) in tea and water samples after simultaneous preconentration of dithizone loaded on naphthalene

A simultaneous preconcentration procedure for the determination of Cd(II), Ni(II), Co(II) and Cu(II) by atomic absorption spectrometry is described. The method is based on solid phase extraction of the metal ions on dithizone loaded on naphthalene in a mini-column, elution with nitric acid and determination by flame atomic absorption spectrometry. The sorption conditions including NaOH concentration, sample volume and the amount of dithizone were optimized in order to attain the highest sensitivity. The calibration graph was linear in the range of 0.5–75.0 ng ml^?1 for Cd(II), 1.0–150.0 ng ml^?1 for Ni(II), 1.0–150.0 ng ml^?1 for Co(II) and 1.0–125.0 ng ml^?1 for Cu(II) in the initial solution. The limit of detection based on 3S_b was 0.13, 0.32, 0.33 and 0.43 ng ml^?1 for Cd(II), Ni(II), Co(II) and Cu(II), respectively. The relative standard deviations (R.S.D) for ten replicate measurements of 20 ng ml^?1of Cd(II), 100 ng ml^?1 of Ni(II), Co(II) and 75 ng ml^?1 of Cu(II) were 3.46, 2.43, 2.45 and 3.26%, respectively. The method was applied to the determination of Cd(II), Ni(II), Co(II) and Cu(II) in black tea, tap and river water samples.     

Preconcentration of Trace Cadmium (II) and Copper (II) in Environmental Water Using a Column Packed with Modified Silica Gel-Chitosan Prior to Flame Atomic Absorption Spectrometry Determination

A new column loaded with modified silica gel-chitosan is proposed as a preconcentration system for adsorption of trace cadmium (II) and copper (II). The optimization steps were performed under dynamic conditions, involving pH, sample flow rate, eluent selection, concentration, volume, and flow rate. Trace Cd(II) and Cu(II) were quantitatively adsorbed by the modified silica gel-chitosan. The metal ions adsorbed on the separation column were eluted with 0.1 M HNO₃ and determined by flame atomic absorption spectrometry. Under the optimum conditions, this method allowed the determination of cadmium and copper with limits of detection (LOD) of 20 ng L^?1 and 38 ng L^?1, respectively. The relative standard deviation values (RSDs) for 1.0 mg L^?1 of cadmium and 1.0 mg L^?1 of copper were 2.62% and 2.85%, respectively.     

Highly Selective and Sensitive Preconcentration of Mercury Ion and Determination by Cold Vapor Atomic Absorption Spectroscopy

Abstract

A simple and selective method based on a sodium dodecyl sulfate (SDS)–coated chromosorb P modified by 2‐mercaptobenzoxazole (MBO) has been developed to selectively separate and concentrate ultra trace amounts of mercury(II) ions for its highly sensitive measurement by cold vapor atomic absorption spectrometry (CVAAS).

The mercury ions were adsorbed quantitatively on SDS‐coated chromosorb due to its complexation with MBO, while the retained Hg²⁺ ions were then stripped from the column with minimal amounts of 2 M nitric acid in acetone. The eluting solution was sent to CV‐AAS for evaluating Hg²⁺ ion content and results indicate that the calibration curve was linear for Hg²⁺ ion in the range of 0.05–85.6 ng mL^?1 and 0.09–9.6 µg mL^?1 of Hg²⁺ ions. Maximum capacity of the SDS‐coated chromosorb modified with 40 mg of the ligand was found to be 498±30 µg of mercury(II), the limit of detection was 0.01 ng mL^?1, and enrichment factors were about 300, which make it suitable it for dilute solution analysis. The method was successfully applied to the determination of Hg²⁺ ion content in real samples.     

A Novel Fluorescent Aminoacid Designed for Fluorometric Detection of Cu （Ⅱ）

A fluorescent aminoacid was designed for selective and sensitive detection of Cu(II) in aqueous solution. The designing of this Cu(II) fluorescent chemosensing molecule, N ± (1‐naphthyl). aminoacetic acid (NAA), was based on the binding of Cu(II) to aminoacetic acid and the novel charge transfer photophysics of 1‐aminonaphthalenes. The fluorescence of NAA was found quenched by Cu (II) and several other metal ions of similar electronic structure such as Co(II), Ni(II) and Zn(II). The quenching was shown to occur via electron transfer within the metal‐NAA complex, which required an optimal combination of high binding affinity and favorable redox properties of the components in the metal‐NAA complex and hence afforded selective fluorometric detection of Cu(II). The calibration graph obeyed Stern‐Volmer theory and was shown for Cu(II) over the range of 0–2.75 ± 10–⁴ mol/L. The quenching constant of Cu(II) was measured as 8.0 ± 10³ mol/L that was two orders of magnitude higher than those of Co(II), Ni(II) and Zn(II). The 3SD limit of detection for Cu(II) was 8.00 ± 10^?6 mol/L with a coefficient of variation of 1.65%. Linear range for quantitative detection of Cu(II) was 2.67 ± 10^?5‐2.75 ± 10^?4 mol/L. The method was applied to synthetic sample measurements which gave recoveries of 105%‐112%.     

Amberlite XAD-7 impregnated with Xylenol Orange: a chelating collector for preconcentration of Cd(II), Co(II), Cu(II), Ni(II), Zn(II) and Fe(III) ions prior to their determination by flame AAS

A new chelating resin, Xylenol Orange coated Amberlite XAD-7, was prepared and used for preconcentration of Cd(II), Co(II), Cu(II), Fe(III), Ni(II) and Zn(II) prior to their determination by flame atomic absorption spectrophotometry. The optimum pH values for quantitative sorption of Cd(II), Co(II), Cu(II), Fe(III), Ni(II) and Zn(II) are 4.5–5.0, 4.5, 4.0–5.0, 4.0, 5.0 and 5.0–7.0, respectively, and their desorptions by 2 mol L^–1 HCl are instantaneous. The sorption capacity of the resin has been found to be 2.0, 2.6, 1.6, 1.6, 2.6 and 1.8 mg g^–1 of resin for Cd, Co, Cu, Fe, Ni and Zn, respectively. The tolerance limits of electrolytes, NaCl, NaF, NaI, NaNO₃, Na₂SO₄ and of cations, Mg²⁺ and Ca²⁺ in the sorption of the six metal ions are reported. The preconcentration factor was between 50 and 200. The t_1/2 values for sorption are found to be 5.3, 2.9, 3.2, 3.3, 2.5 and 2.6 min for the six metals, respectively. The recoveries are between 96.0 and 100.0% for the different metals at preconcentration limits between 10 to 40 ng mL^–1. The preconcentration method has been applied to determine the six metal ions in river water samples after destroying the organic matter (if present in very large amount) with concentrated nitric acid (RSD ≤ 8%, except for Cd for which it is upto 12.6%) and cobalt content of vitamin tablets with RSD of ～ 3.0%.     

Chemically modified multiwalled carbon nanotubes as efficient and selective sorbent for separation and preconcentration of trace amount of Co(II), Cd(II), Pb(II), and Pd(II)

Multi-walled carbon nanotubes (MWCNTs) were chemically functionalized by glutaric dihydrazide (GDH) and characterized with FT-IR technique. This new sorbent was used for enrichment and preconcentration of Co(II), Cd(II), Pb(II), and Pd(II) ions. The adsorption was achieved quantitatively on MWCNTs at pH 4.0, and then the retained metal ions on the adsorbent were eluted with 1.5 mol L^?1 HNO₃. The effects of analytical parameters including pH of the solution, eluent type, sample volume, and matrix ions were investigated for optimization of the presented procedure. The adsorption capacity of the adsorbent at optimum conditions was found to be 33.6, 29.2, 22.1, and 36.0 mg g^?1 for Co(II), Cd(II), Pb(II), and Pd(II), respectively. The LOD values of the method were 0.16, 0.19, 0.17, and 0.12 ng mL^?1 (3Sb, n = 10) for Co(II), Cd(II), Pb(II), and Pd(II), respectively. The RSDs values of the method were 0.75, 0.85, 1.16, and 1.30 ng mL^?1 for Co(II), Cd(II), Pb(II), and Pd(II), respectively. The method was applied for the determination of analytes in soil, well water, and wastewater samples with satisfactory results.     

Simultaneous separation and preconcentration of trace amounts of copper (II), cobalt (II) and silver (I) by modified Amberlyst®15 resin

A solid phase extraction method for simultaneous preconcentration and separation of trace amounts of copper, cobalt and silver in different samples, using a column packed with modified Amberlyst®15 resin is developed. Amberlyst®15 resin was modified with 5-(4-dimethylaminobenzylidene)rhodanine and then the modified resin was used as a support material for the solid phase extraction and preconcentration of Cu(II), Co(II) and Ag(I) ions from aqueous solution in the pH range 3.5–4.5. The adsorbed metal ions on the column were quantitatively eluted with a 7% thiourea solution prepared in 2?mol?L^?1 HNO₃, which were detected by flame atomic absorption spectrometry. The effects of analytical parameters including pH of the solution, eluent type, flow rate of samples, eluent and matrix ions were investigated for optimization of the presented procedure. The detection limits were 2.1, 0.9 and 0.9?ng?mL^?1 for Cu(II), Co(II) and Ag(I) ions, respectively based on the three times the standard deviations of the blanks. The preconcentration factor was 112.5. The calibration graphs were obtained in the ranges of 0.05 to 10.0, 0.03 to 13.0 and 0.04 to 9.0?µg?mL^?1 for Cu(II), Co(II) and Ag(I) ions concentrations, respectively. Relative standard deviations (n?=?7) for Cu(II), Co(II) and Ag(I) ions were found ±2.5 %, ±0.84% and ±3.8% respectively. The method was applied to the determination of mentioned ions in well water, waste water and lettuce sample.     

Removal, preconcentration and spectrophotometric determination of U(VI) from water samples using modified maghemite nanoparticles

Arsenazo III modified maghemite nanoparticles (A-MMNPs) was used for removing and preconcentration of U(VI) from aqueous samples. The effects of contact time, amount of adsorbent, pH and competitive ions was investigated. The experimental results were fitted to the Langmuir adsorption model in the studied concentration range of uranium (1.0 × 10^?4–1.0 × 10^?2 mol L^?1). According to the results obtained by Langmuir equation, the maximum adsorption capacity for the adsorption of U(VI) on A-MMNPs was 285 mg g^?1 at pH 7. The adsorbed uranium on the A-MMNPs was then desorbed by 0.5 mol L^?1 NaOH solution and determined spectrophotometrically. A preconcentration factor of 400 was achieved in this method. The calibration graph was linear in the range 0.04–2.4 ng mL^?1 (1.0 × 10^?10–1.0 × 10^?8 mol L^?1) of U(VI) with a correlation coefficient of 0.997. The detection limit of the method for determination of U(VI) was 0.01 ng mL^?1 and the relative standard deviation (R.S.D.) for the determination of 1.43 and 2.38 ng mL^?1 of U(VI) was 3.62% and 1.17% (n = 5), respectively. The method was applied to the determination of U(VI) in water samples.     

A screen-printed carbon electrode modified with a bismuth film and gold nanoparticles for simultaneous stripping voltammetric determination of Zn(II), Pb(II) and Cu(II)

The authors report on a disposable sensor for the differential pulse anodic stripping voltammetric (DPASV) determination of the ions Zn(II), Pb(II) and Cu(II). Simultaneous detection is accomplished by using a screen-printed carbon electrode (SPCE) co-modified with an in-situ plated bismuth (Bi)) film and gold nanoparticles (AuNPs). The synergistic effect of the Bi film, and the large surface and good electrical conductivity of the AuNPs strongly assist in the co-deposition of the three ions. Four well-defined and fully separated anodic stripping peaks, at 540 mV for Zn(II), 50 mV for Pb(II), 140 mV for Bi(III) and 295 mV for Cu(II), all vs. Ag/AgCl, can be seen. The modified SPCE was characterized by scanning electron microscopy, X-ray diffraction, cyclic voltammetry and electrochemical impedance spectroscopy. Under the optimized conditions, the sensor has a good response to these ions. The detection limits (at an S/N ratio of 3) are 50 ng·L^?1 for Zn(II), 20 ng·L^?1 for Pb(II), and 30 ng·L^?1 for Cu(II). The method was applied to the determination of the 3 ions in spiked lake water samples.

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Graphical abstract Schematic of screen-printed carbon electrode (SPCE) co-modified with a bismuth film and gold nanoparticles for electrochemical simultaneous determination of Zn(II), Pb(II) and Cu(II) by differential pulse anodic stripping voltammetric (DPASV).

     

Selective preconcentration of Lanthanum(III) by Coriolus versicolor immobilised on Amberlite XAD-4 and its determination by ICP-OES

Coriolus versicolor, a wood fungus, was immobilised on Amberlite XAD-4 and used as solid-phase biosorbent for preconcentrations of rare earth elements. La(III), Th(IV), U(IV) and Ce(III) were subjected to solid-phase extraction procedure. We observed that La(III) was selectively preconcentrated, while other ions remained in solution at pH 6.0. 5.0 mL of 1.0 mol L^?1 HCl was used to elaute La(III) from column. 250 mg of C. versicolor loaded on 1000 mg of XAD-4 was optimised as solid-phase matrix. Concentrations of ions in solutions were determined by inductively coupled plasma– optical emission spectrometry (ICP-OES). The calibration plot after preconcentration was linear in the range from 1.0 to 50.0 ng mL^?1 for La(III). Limit of detection was found as 0.27 ng mL^?1 for La(III) by SPE method. Relative standard deviation was found lower than 6.7% for 1.0 ng mL^?1 of La(III) solution (n = 10). The sensitivity of ICP-OES was improved by a factor of 46.8. The applicability of the method was validated through the analysis of certified reference samples of tea (NCS ZC-73014) and spinach (NCS ZC-73013).     

LC-MS-MS Method for Simultaneous Determination of Icariin and Its Active Metabolite Icariside II in Human Plasma

An LC-MS-MS method was revised and validated for simultaneous determination of icariin and its active metabolite icariside II in human plasma. The analytes and daidzein (IS) were extracted by liquid–liquid extraction and analyzed by LC-MS-MS. The separation was performed by a Zorbax SB-C₁₈ column (3.5 μm, 2.1 × 100 mm) with an isocratic mobile phase consisting of methanol–water–formic acid (65:35:0.035, v/v/v) at a flow rate of 0.25 mL min^?1. Detection was performed on a triple quadrupole tandem mass spectrum by multiple reaction monitoring mode using the electrospray ionization technique in positive mode. The method had lower limits of quantitation 0.2 and 0.1 ng mL^?1 for icariin and icariside II, respectively, using 500 μL plasma sample. The linear calibration curves were obtained in the concentration range of 0.2–100 ng mL^?1 for icariin and 0.1–100 ng mL^?1 for icariside II. The RSD values of intra- and inter-day precision calculated from quality control (QC) samples were less than 7.2% for icariin and less than 6.5% for icariside II. The accuracy as determined from QC samples was within 3.8% for each analyte. The method has been applied to determine and evaluate the pharmacokinetic of icariin and its metabolite icariside II in volunteers following oral administration of icariin and extract of Epimedium, respectively.