Pranav Shrivastav

A solvent extraction separation of uranium with a new crown hydroxamic acid 5, 14-N, N′-hydroxyphenyl-4, 15-dioxo-1,5,14,18-tetraaza hexacosane (NHDTAHA) in the presence of cerium, thorium and lanthanides is described. The uranium is extracted with chloroform solution of NHDTAHA and the extract is directly used for GS-AAS measurements. The detection limit is 0.01 ppm with a sensitivity of 20 ng/0.005 absorbance of uranium. The extraction constants of uranium crown hydroxamic acid complexes are determined. The selectivity factors (Kuranyl/Kn+M) for uranium crown hyrdoxamate evaluated by comparing the Kuranyl with the stability constants for competing metal cations (Kn+M) and anions (KnA−) and were found to be remarkably large. Uranium is preconcentrated and also determined spectrophotometrically. The molar absorptivity is 1.0×104 l−1 mol−1 per cm at 390 nm and system obeys Beer’s law in the range 2.0–30 ppm of uranium. Uranium has been determined in standard and environmental samples.

A simple, precise and accurate assay for the determination of 6-methoxy-2-naphthylacetic acid (6-MNA), an active metabolite of nabumetone in human plasma, was developed and validated using liquid chromatography–tandem mass spectrometry (LC-MS/MS). The analyte (6-MNA) and propranolol (internal standard, IS) were extracted from 200 µL aliquot of human plasma via solid-phase extraction employing HLB Oasis cartridges and separated on a Discovery® HS C18 (50 × 4.6 mm, 5 µm) column. Detection of analyte and IS was done by tandem mass spectrometry with a turbo ion spray interface operating in positive ion and multiple reaction monitoring acquisition mode. The total chromatographic runtime was 3.0 min with retention time for 6-MNA and IS at 1.97 and 1.26 min, respectively. The method was validated over a dynamic linear range of 0.20–60.00 µg/mL for 6-MNA with mean correlation coefficient r ≥ 0.9986. The intra-batch and inter-batch precision (%CV) across five validation runs (lower limit of quantiation, low-, medium- and high-quality controls and upper limit of quantitation) was less than 7.5%. The accuracy determined at these levels was within −5.8 to +0.2% in terms of percentage bias. The method was successfully applied for a bioequivalence study of 750 mg nabumetone tablet formulation in 12 healthy Indian male subjects under fasted condition. Copyright © 2008 John Wiley & Sons, Ltd.

A new crown hydroxamic acid, 5,14-N,N′-hydroxyphenyl-4,15-dioxo-1,5,14,18-tetraaza hexacosane (NHDTAHA) for the extraction and spectrophotometric determination of lanthanum(III) is described. Lanthanum(III) forms a yellow coloured complex with NHDTAHA, which is extracted with chloroform, having molar absorptivity 7.7 × 103 1 mol−1 per cm at 372 nm. The system obeys Beer's law in the range 1.2–20 ppm of lanthanum. The extract is directly aspirated for ICP-AES measurements, the limits for estimation are 5–140 ppb of lanthanum. Lanthanum has been determined in monazite sand and standard samples.

New chromogenic supramolecular vanadophiles were designed and synthesized by incorporating hydroxamic acid chains on a 1,3-alternate thiacalix[4]arene scaffold and were found to show high affinity toward vanadate ions. The article describes a comprehensive design process to devise a tailor-made co-ordination cavity for vanadate ions by pre-organization of hydroxamic acid chelating moieties on a 1,3-alternate thiacalix[4]arene scaffold. These receptors simultaneously co-ordinate two vanadate ions giving a highly ‘staggered’ geometry with almost D2d symmetry. Proposed structures and complexation behavior of the receptors were explained by critical examination of FTIR, UV–visible, mass, and 1H NMR data.

A rapid, sensitive and accurate liquid chromatography–tandem mass spectrometry (LC–MS/MS) assay for the simultaneous determination of tramadol and its active metabolite, O-desmethyltramadol in human plasma is developed using propranolol as internal standard (IS). The analytes and IS were extracted from 200 μL aliquots of human plasma via protein precipitation using acetonitrile. Chromatographic separation was achieved in a run time of 2.0 min on an Aquasil C18 (100 mm × 2.1 mm, 5 μm) column under isocratic conditions. Detection of analytes and IS was done by tandem mass spectrometry, operating in positive ion and multiple reaction monitoring (MRM) acquisition mode. The method was fully validated for its selectivity, sensitivity, linearity, precision and accuracy, recovery, matrix effect, ion suppression/enhancement, stability and dilution integrity. A linear dynamic range was established from 1.0 to 600.0 ng/mL for tramadol and 0.5–300.0 ng/mL for O-desmethyltramadol. The method was successfully applied to a bioequivalence study of 200 mg tramadol tablet formulation in 27 healthy Indian male subjects under fasting condition.

The effect of nitrogen as the collision-activated dissociation (CAD) gas on the fragmentation of dipyridamole was investigated in the range of 10–90 eV collision energy. The results support the collision model reported elsewhere, that the degree of ion fragmentation increases with the increasing mass of the collision gas. A simple, sensitive and high-throughput liquid chromatography/tandem mass spectrometry (LC/MS/MS) method has been developed for the determination of dipyridamole, a platelet aggregation inhibitor in human plasma, using granisetron as internal standard (IS). The method involved liquid–liquid extraction of the analyte and IS from 0.5 mL human plasma with diethyl ether. The chromatographic separation was achieved under isocratic conditions and the ion transitions for dipyridamole (m/z 505.40 → 429.60) and the IS (m/z 313.10 → 138.20) were monitored on a triple quadrupole mass spectrometer, operating in positive ion multiple reaction monitoring (MRM) mode. The method was validated over the concentration range 5.1–4499.1 ng/mL for dipyridamole. The method was rugged and rapid with a total run time of 1.2 min. It was successfully applied to a pivotal bioequivalence study in 67 healthy human subjects after oral administration of a 75 mg extended release formulation under fasting condition. Copyright © 2008 John Wiley & Sons, Ltd.

A rapid, simple and sensitive liquid chromatography tandem mass spectrometry (LC–MS/MS) assay for simultaneous determination of venlafaxine (VEN) and its active metabolite, O-desmethylvenlafaxine (ODV) in human plasma was developed using nadolol as internal standard (IS). The analytes and IS were extracted from 200 μl aliquots of human plasma via protein precipitation using 0.43% formic acid in acetonitrile and separated on a Hypurity cyano (50 mm × 4.6 mm, 5 μm) column. Quantitation was performed on a triple quadrupole mass spectrometer employing electrospray ionization technique, operating in multiple reaction monitoring (MRM) and positive ion mode. The precursor to product ion transitions monitored for VEN, ODV and IS were m/z 278.3 → 58.1, 264.3 → 58.1 and 310.4 → 254.1, respectively. The total chromatographic runtime was 3 min with retention time for VEN, ODV and IS at 1.93, 1.50 and 1.29 min, respectively. The method was fully validated for its sensitivity, accuracy and precision, linearity, recovery, matrix effect, dilution integrity and stability studies. The linear dynamic range of 2.0–500 ng/ml was established for both VEN and ODV with mean correlation coefficient (r), 0.9994 and 0.9990, respectively. The intra-batch and inter-batch precision (%CV) in three validation batches across five concentration levels (LLOQ, LQC, MQC, HQC and ULOQ) was less than 12.6% for both the analytes. The accuracy determined at these levels was within −9.8 to +3.9% in terms of %bias. The method was successfully applied to a bioequivalence study of 150 mg venlafaxine extended release capsule formulation in 22 healthy Indian male subjects under fed condition.

A very stable calixarene-based polymeric chelating resin has been synthesized by covalently linking calix[4]arene-o-vanillinthiosemicarbazone through its ‘lower rim’ to Merrifield resin. It was characterized by FT IR, 1H NMR and elemental analysis. The resin was efficiently employed to separate and preconcentrate toxic metal ions such as Cu(II), Cd(II) and Pb(II) in a column prior to their determination by UV-Vis spectrophotometry and atomic absorption spectrophotometry (GFAAS) with a relative standard deviation ranging between 1.0–1.4%. Various physico-chemical parameters such as pH, concentration of eluting agents, flow rate, total sorption capacity, metal-ligand stoichiometry, exchange kinetics, preconcentration factor, distribution coefficient, breakthrough capacity, resin stability, effect of electrolytes and associated metal ions have been studied. Uptake and stripping of these metal ions on the resin were fast, indicating better access of the metal ions to the chelating sites. Detection limits (3σB) of 4.22 µg L−1, 11.89 µg L−1 and 19.61 µg L−1, along with preconcentration factors of 100, 125 and 111 for Cu(II), Cd(II) and Pb(II), respectively, were achieved. The proposed method was successfully applied to the separation and trace determination of Cu(II), Cd(II) and Pb(II) from natural water samples of Ahmedabad city.

A high throughput and rugged ultra performance liquid chromatography tandem mass spectrometry (UPLC–ESI-MS/MS) method is developed and validated for the selective determination of protease inhibitors – lopinavir (LPV) and ritonavir (RTV) in human plasma. Plasma samples were prepared by solid phase extraction of the analytes and their deuterated analogs as internal standard (IS) using Waters Oasis HLB cartridges. The chromatographic separation was achieved in a run time of 1.2 min on Waters Acquity UPLC BEH C18 column (50 mm × 2.1 mm, 1.7 μm) under isocratic conditions. The mobile phase consisted of 10 mM ammonium formate, pH 4.0 adjusted with formic acid and methanol (10:90, v/v). The protonated precursor → product ion transitions for lopinavir, ritonavir, d8-lopinavir and d6-ritonavir were monitored on a triple quadrupole mass spectrometer, operating in the multiple reaction monitoring (MRM) and positive ion mode. A linear dynamic range of 2.9–1452 ng/mL and 29.6–14379 ng/mL was established for ritonavir and lopinavir respectively using 0.1 mL human plasma. The mean relative recovery of lopinavir (96.6%), ritonavir (97.5%), d8-lopinavir (85.5%) and d6-ritonavir (86.3%) from spiked plasma samples was consistent and reproducible. The method was successfully applied to a bioequivalence study of [200(lopinavir) + 50(ritonavir)] mg tablet formulation in 36 healthy human subjects under fasting conditions.

This Letter reports the results of our studies towards the synthesis of thiacalixarenes. In an effort to develop an efficient and inexpensive synthetic methodology for thiacalixarenes, several trials were conducted to study the effect of base/template, solvents, catalyst, phenol substitutions and temperature profile. Microwave synthesis was also tested to reduce the overall time for the reaction. Based on the results of these investigations, a detailed reaction mechanism is proposed and an optimized synthetic procedure for p-tert-butylthiacalix[4]arene is demonstrated.

A high throughput bioanalytical method based on solid phase extraction and liquid chromatography–tandem mass spectrometry (LC–MS/MS), has been developed for the estimation of perindopril and its metabolite perindoprilat, an angiotensin-converting enzyme inhibitor in human plasma. Ramipril was used as internal standard (IS). The extraction of perindopril, perindoprilat and ramipril from the plasma involved treatment with phosphoric acid followed by solid phase extraction (SPE) using hydrophilic lipophilic balance HLB cartridge. The SPE eluate without drying were analyzed by LC–MS/MS, equipped with turbo ion spray (TIS) source, operating in the negative ion and selective reaction monitoring (SRM) acquisition mode to quantify perindopril and perindoprilat in human plasma. The total chromatographic run time was 1.5 min with retention time for perindopril, perindoprilat and ramipril at 0.33, 0.35 and 0.30 min. The developed method was validated in human plasma matrix, with a sensitivity of 0.5 ng/ml (CV, 7.67%) for perindopril and 0.3 ng/ml (CV, 4.94%) for perindoprilat. This method was extensively validated for its accuracy, precision, recovery, stability studies and matrix effect especially because the pattern of elution of all the analytes appears as flow injection elution. Sample preparation by this method yielded extremely clean extracts with very good and consistent mean recoveries; 78.29% for perindopril, 76.32% for perindoprilat and 77.72% for IS. The response of the LC–MS/MS method for perindopril and perindoprilat was linear over the range 0.5–350.0 ng/ml for perindopril and 0.3–40 ng/ml for perindoprilat with correlation coefficient, r ≥ 0.9998 and 0.9996, respectively. The method was successfully applied for bioequivalence studies in human subjects samples with 4 mg immediate release (IR) formulations.

The present study was an attempt to investigate the hepatoprotective and antioxidative property of Phyllanthus amarus (P. amarus) extract and phyllanthin. Phyllanthin, one of the active lignin present in this plant species was isolated from the aerial parts, by silica gel column chromatography employing gradient elution with hexane–ethyl acetate solvent mixture. It was obtained in high yields (1.23%), compared to reported procedures and the purity was ascertained by HPTLC and reversed-phase HPLC analysis. Characterization of phyllanthin was done by mp, UV–Visible spectrophotometry, elemental analysis, FT-IR, 1H NMR, 13C NMR and mass spectral analysis. Free radical scavenging activity of P. amarus extract and phyllanthin was also examined using DPPH assay. The protective effect of P. amarus extract and phyllanthin was studied on CCl4-induced toxicity in human hepatoma HepG2 cell line. The results indicated that CCl4 treatment caused a significant decrease in cell viability. In addition, the toxin treatment initiated lipid peroxidation (LPO), caused leakage of enzymes like alanine transaminase (ALT) and lactate dehydrogenase (LDH) with a significant decrease in glutathione (GSH) levels. It was observed that phyllanthin effectively alleviated the changes induced by CCl4 in a concentration-dependent manner, with much smaller strengths as compared to P. amarus extract.

A rapid, specific and sensitive LC-MS/MS assay using solid-phase extraction (SPE) for the determination of pravastatin, in human plasma is described. The plasma filtrate obtained after SPE, using a polymer base, a hydrophilic–lipophilic balance (HLB) cartridge, was submitted directly to short-column liquid chromatography–tandem mass spectrometric (LC-MS/MS) assay, with negligible matrix effect on the analysis. For validation of the method, the recovery of the free analytes was compared with that from an optimized extraction method, and the analyte stability was examined under conditions mimicking the sample storage, handling, and analysis procedures. The extraction procedure yielded extremely clean extracts with a recovery of 107.44 and 98.93% for pravastatin and IS, respectively. The intra-assay and inter-assay precisions for the samples at the LLOQ were 3.30 and 7.31% respectively. The calibration curves were linear for the dynamic range 0.5–200 ng/mL with correlation coefficient r ≥ 0.9988. The intra- and inter-assay accuracy ranged from 95.87 to 112.40%. The method is simple and reliable with a total run time of 3 min. This novel validated method was applied to the pharmacokinetic (PK) study in human volunteers receiving a single oral dose of 40 mg immediate release (IR) formulation. Copyright © 2006 John Wiley & Sons, Ltd.

A rapid and sensitive liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) method for the determination of isosorbide-5-mononitrate (5-ISMN), used in the treatment of angina pectoris, in human plasma is described. The quantification of 5-ISMN was performed via stable acetate adduct formation with a high relative abundance. The plasma filtrate obtained after solid-phase extraction (SPE), using a polymer based, hydrophilic-lipophilic balanced (HLB) cartridge, was submitted directly to reversed-phase high-performance liquid chromatography separation followed by ESI and detection of the resulting ions using triple-quadrupole mass spectrometry in selected reaction monitoring (SRM) mode. There was no significant matrix effect on the analysis. For validation of the method, the recovery of the free analyte response was compared to that obtained from an optimized extraction method. The analyte stability was examined under conditions mimicking the sample storage, handling, and analytical procedures. The extraction procedure yielded extremely clean extracts with a recovery of 95.51% and 93.98% for iossorbide-5-mononitrate and topiramate (internal standard (IS)), respectively. The calibration curves were linear for the dynamic range of 10.0 to 1000.0 ng/mL with a correlation coefficient r ≥ 0.9985. The intra-assay and inter-assay precision for the samples at the lower limit of quantification (LLOQ) were 9.02 and 13.30%, respectively. The intra-assay accuracies at LLOQ, LQC, MQC and HQC levels varied from 98.13 to 118.15, 102.34 to 105.21, 100.69 to 109.68, and 95.76 to 102.92%, respectively, while the inter-assay accuracies ranged from 93.10 to 118.15, 93.03 to 107.04, 86.97 to 109.68 and 86.18 to 105.85%, respectively, at these levels. The method is rugged and fast with a total run time of 2 min. The method was successfully applied for a bioequivalence study in 24 human subject samples after oral administration of 60 mg extended release (ER) formulations. Copyright © 2006 John Wiley & Sons, Ltd.

A high-throughput and sensitive bioanalytical method using liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) has been developed for the estimation of sibutramine and its two metabolites (M1 and M2). The extraction of sibutramine, its metabolites and imipramine (internal standard (IS)) from the plasma involved treatment with phosphoric acid followed by solid-phase extraction (SPE) using a hydrophilic-lipophilic balanced HLB cartridge. The SPE eluate without drying and reconstitution was analyzed by LC/MS/MS, equipped with a with turbo ion spray (TIS) source, operating in the positive and multiple reaction monitoring (MRM) acquisition mode. Sample preparation by this method yielded extremely clean extracts with quantitative and consistent mean recoveries; 95.12% for sibutramine, 92.74% for M1, 95.97% for M2 and 96.60% for the IS. The total chromatographic run time was 3.0 min with retention times of 2.51, 2.13, 2.09 min for sibutramine, M1, M2 and imipramine, respectively. The developed method was validated in human plasma matrix, with a sensitivity of 0.1 ng/mL (coefficient of variance (CV), 2.07%) for sibutramine, 0.1 ng/mL (CV, 3.59%) for M1 and 0.2 ng/mL (CV, 4.93%) for M2. Validation of the method for its accuracy, precision, recovery, matrix effect and stability was carried out especially with regard to real subject sample analysis. The response was linear over the dynamic range 0.1 to 8.0 ng/mL for sibutramine and M1, and 0.2 to 16.0 ng/mL for M2 with correlation coefficients of r ≥ 0.9959 (sibutramine), 0.9935 (M1) and 0.9943 (M2). The method was successfully applied for bioequivalence studies in 40 human subjects with 15 mg capsule formulations. Copyright © 2006 John Wiley & Sons, Ltd.

A selective and high throughput liquid chromatography/tandem mass spectrometry (LC–MS/MS) method has been developed and validated to separate, detect and simultaneously quantify lamivudine (3TC), stavudine (d4T) and nevirapine (NVP) in human plasma using metaxalone as internal standard (IS). After solid phase extraction (SPE), the analytes and the IS were chromatographed on a Symmetry C18 (150 mm × 3.9 mm i.d., 5 μm particle size) column using 5 μL injection volume with a run time of 4.5 min. An isocratic mobile phase consisting of 0.5% glacial acetic acid in water:acetonitrile (20:80, v/v) was used to separate all these drugs. The precursor and product ions of these drugs were monitored on a triple quadrupole mass spectrometer, operating in the multiple reaction monitoring mode (MRM) without polarity switch. The method was validated over the range of 25–3000 ng/mL for 3TC, 20–2000 ng/mL for d4T and 50–5000 ng/mL for NVP. The absolute recoveries for analytes (≥86%) and IS (98.12%) achieved from spiked plasma samples were consistent and reproducible. Inter-batch and intra-batch precision (%CV) across four validation runs (LLOQ, LQC, MQC and HQC) was less than 10. The accuracy determined at these levels was within ±8% in terms of relative error. The method was successfully applied to a pivotal bioequivalence study of [60 (3TC) + 12 (d4T) + 100 (NVP)] mg dispersible tablets in 60 healthy human subjects under fasting condition.

A new calix[4]resorcinarene bearing eight hydroxamic acid groups (C4RAHA) has been synthesized and characterized by FT-IR, 1H-NMR and elemental analysis. Its analytical properties were investigated, and showed high affinity and selectivity toward thorium(IV) in the presence of large quantities of associated metal ions. Thorium(IV) was extracted from an ethyl acetate solution of C4RAHA at pH 4.5. The lambdamax and molar absorptivity (epsilon) for thorium(IV) were 341 nm and 7120 l mol(-1) cm(-1). The complexation of thorium(IV) with C4RAHA has a 4:1 metal:ligand stoichiometry, which is relatively rare. The extracts were directly aspirated in the plasma for ICP-AES measurements for thorium(IV) in the presence of a diversified matrix. The system obeyed Beer's law over the range 0.1 - 6.5 microg ml(-1) of thorium(IV) with a Sandell sensitivity of 0.0325 microg cm(-2). The preconcentration factor and overall stability constant evaluated at 25 degrees C for thorium(IV) were 133 and 15.86, respectively. The complexation was characterized by a favorable enthalpy change. A liquid-membrane transport study of thorium(IV) was carried out from the source to the receiving phase under controlled conditions, and a mechanism of transport proposed. To check the validity of the proposed method, thorium(IV) was determined in monazite sand, rare earth sand and water samples.

A simple and rapid liquid chromatography/tandem mass spectrometry (LC–MS/MS) method has been developed and validated for the simultaneous quantitation of antidiabetic drugs metformin and glyburide in human plasma using glimepiride as internal standard (IS). After acidic acetonitrile-induced protein precipitation of the plasma samples, metformin, glyburide and IS were chromatographed on reverse phase C18 (50 mm × 4.6 mm i.d., 5 μm) analytical column. Quantitation was performed on a triple quadrupole mass spectrometer employing electrospray ionization technique and operating in multiple reaction monitoring (MRM) and positive ion mode. The total chromatographic run time was 3.5 min and calibration curves were linear over the concentration range of 20–2500 ng/ml for metformin and 5–500 ng/ml for glyburide. The method was validated for selectivity, sensitivity, recovery, linearity, accuracy and precision, dilution integrity and stability studies. The recoveries obtained for the analytes and IS (≥69%) were consistent and reproducible. Inter-batch and intra-batch coefficient of variation across four validation runs (LLOQ, LQC, MQC and HQC) was less than 8%. The accuracy determined at these levels was within ±8% in terms of relative error (RE). The method was applied to a bioequivalence study of 500 mg metformin and 5 mg of glyburide tablet after oral administration to 28 healthy human subjects under condition of fasting.

The first liquid chromatography/tandem mass spectrometry (LC/MS/MS) method for the determination of levetiracetam, an antiepileptic drug, in human plasma is described. The plasma filtrate obtained after solid-phase extraction (SPE), using a polymer-based, hydrophilic-lipophilic balanced (HLB) cartridge, was submitted directly to a short column LC/MS/MS assay. There was no significant matrix effect on the analysis. For validation of the method, the recovery of the free analytes was compared to that from an optimized extraction method, and the analyte stability was examined under conditions mimicking sample storage, handling, and analytical procedures. The extraction procedure yielded extremely clean extracts with a recovery of 79.95% and 89.02% for levetiracetam and the internal standard (IS), respectively. The intra-assay and inter-assay precision for the samples at the lower limit of quantitation (LLOQ) were 6.33 and 6.82%, respectively. The calibration curves were linear for the dynamic range of 0.5 to 50 µg/mL with a correlation coefficient r ≥ 0.9971. The intra-assay accuracy at LLOQ, LQC, MQC, and HQC levels ranged from 81.60 to 95.40, 93.00 to 103.47, 95.97 to 104.09, and 91.15 to 95.18%, respectively, while the inter-assay accuracy at LLOQ, LQC, MQC and HQC levels varied from 80.20 to 95.40, 88.53 to 107.53, 95.97 to 108.45, and 91.15 to 112.70%, respectively. The method is rugged and fast with a total instrumental run time of 2 min. The method was successfully applied for bioequivalence studies in human subject samples after oral administration of 1000 mg immediate release (IR) formulations. Copyright © 2006 John Wiley & Sons, Ltd.

A new chelating polymeric sorbent is developed using Merrifield chloromethylated resin anchored with calix[4]arene-o-vanillinsemicarbazone for simultaneous separation and solid phase extractive preconcentration of U(VI) and Th(IV). The “upper-rim” functionalized calix[4]arene-o-vanillinsemicarbazone was covalently linked to Merrifield resin and characterized by FT-IR and elemental analysis. The synthesized chelating polymeric sorbent shows superior binding affinity towards U(VI) and Th(IV) under selective pH conditions. Various physico-chemical parameters that influence the quantitative extraction of metal ions were optimized. The optimum pH range and flow rates for U(VI) and Th(IV) were 6.0–7.0 and 1.0–4.0 ml min−1 and 3.5–4.5 and 1.5–4.0 ml min−1, respectively. The total sorption capacity found for U(VI) and Th(IV) was 48734 and 41175 μg g−1, respectively. Interference studies carried out in the presence of diverse ions and electrolyte species showed quantitative analyte recovery (98–98.5%) with lower limits of detection, 6.14 and 4.29 μg l−1 and high preconcentration factors, 143 and 153 for U(VI) and Th(IV), respectively. The uptake and stripping of these metal ions on the resin were fast, indicating a better accessibility of the metal ions towards the chelating sites. The analytical applicability of the synthesized polymeric sorbent was tested with some synthetic mixtures for the separation of U(VI) and Th(IV) from each other and also from La(III), Cu(II) and Pb(II) by varying the pH and sequential acidic elution. The validity of the proposed method was checked by analyzing these metal ions in natural water samples, monazite sand and standard geological materials.

A very stable chelating resin matrix was synthesized by covalently linking o-vanillinthiosemicarbazone (oVTSC) with the benzene ring of the polystyrene-divinylbenzene resin Amberlite XAD-2 through a -NN- group. The resin was used successfully for the separation and preconcentration of copper(II), zinc(II) and lead(II) prior to their determination by atomic absorption spectrophotometry. The total sorption capacity of the resin was 850, 1500 and 2000 μg g−1 of the resin for Cu(II), Zn(II) and Pb(II), respectively. For the quantitative sorption and recovery of Cu(II), Zn(II) and Pb(II), the optimum pH and eluants were pH 2.5–4.0 and 4 M HCl or 2 M HNO3 for Cu(II), pH 5.5–6.5 and 1.0–2.0 M HCl for Zn(II) and pH 6.0–7.5 and 3 M HCl or 1 M HNO3 for Pb(II). Both, the uptake and stripping of these metal ions were fairly rapid, indicating a better accessibility of the chelating sites. The values for Cu(II), Zn(II) and Pb(II) were also determined. Limit of tolerance of some electrolytes like NaCl, NaF, NaNO3, Na2SO4 and Na3PO4 have been reported. The preconcentration factor for Cu(II), Zn(II) and Pb(II) was 90, 140 and 100 respectively. The method was applied for the determination of Cu(II), Zn(II) and Pb(II) in the water samples collected from Sabarmati river, Ahmedabad, India.

A method for the determination of sertraline, a new antidepressant drug and a selective serotonin reuptake inhibitor (SSRI), in human plasma is described. Therapeutic drug monitoring (TDM) necessitates efficient, fast and reliable analytical methods validated by external quality control. We therefore devised a simple, rapid and sensitive isocratic reversed-phase liquid chromatographic-tandem mass spectrometric method equipped with Turbo Ion spray (TIS) source, operating in the positive ion and selective reaction monitoring (SRM) acquisition mode to quantify sertraline in human plasma. A new and superior procedure of solid-phase extraction (SPE) (compared to liquid–liquid extraction) was followed to extract sertraline and imipramine as internal standard (IS) from the human plasma. Sample preparation was performed using waters hydrophilic–lipophilic balance (HLB) cartridge and this method yielded extremely clean extracts with very good recovery, 81.47 and 85.79% for sertraline and IS, respectively. Both were analyzed by combined reverse phase liquid chromatography and tandem mass spectrometry (LC–MS/MS) with positive ion TIS ionization using SRM acquisition mode. The response of the LC–MS/MS method for sertraline was linear over the dynamic range of 0.5–60.0 ng/ml with correlation coefficient r ≥ 0.9996. The coefficient of variance (%CV) was 8.53% at 0.5 ng/ml and the accuracy was well within the accepted limit of ±20% at lower limit of quantification (LLOQ) and ±15% at all the other concentrations in the linear range. This method was fully validated for the accuracy, precision and stability studies. The above findings indicate that the method is very much accurate and precise and can be successfully applied for bioequivalence studies in human subjects.

A nonionic polymeric adsorbent styrene divinylbenzene, Amberlite XAD-4 was functionalized with o-vanillinsemicarbazone and its analytical properties have been studied. The synthesized resin was utilized for selective column separation, pre-concentration and trace determination of lanthanum(III) (La(III)), cerium(III) (Ce(III)), thorium(IV) (Th(III)) and uranium(VI) (U(VI)). The resin exhibits good chemical stability, reusability and faster rate of equilibrium for their determination by spectrophotometry and their simultaneous confirmation of the results by inductively coupled plasma-atomic emission spectrometry (ICP-AES) and graphite furnace-atomic absorption spectrometry (GF-AAS). Both, the uptake and stripping of these metal ions were fairly rapid, indicating a better accessibility of the chelating sites. The proposed method has been applied to sequential chromatographic separation of their binary and ternary mixtures. Uranium(VI) has been determined from simulated river water sample with good analytical reliability. The detection limit of these metal ions on the resin is 100 ng cm−3 with recovery upto 96–98%. The method is also applied for their determination in monazite sand and some standard geological materials.

The new “upper-rim” functionalized 11,23-disemicarbazono-26,28-n-dipropoxy-25,27-dihydroxy calix[4]arene has been synthesized by condensing 11,23-diformyl-26,28-n-dipropoxy-25,27-dihydroxy calix[4]arene with semicarbazide hydrochloride. This calix[4]arene-semicarbazone derivative was then covalently linked with commercially available Merrifield’s peptide resin at the “lower-rim” to obtain polymeric chelating resin and its analytical properties were investigated. The resin was then used successfully for the separation and preconcentration of lanthanum(III), cerium(III), thorium(IV) and uranium(VI) prior to their determination by spectrophotometry and inductively coupled plasma atomic emission spectroscopy. The resin exhibits good separating ability with maximum sorption between pH 2.5–4.5 for Th(IV) and between pH 5.5–7.0 for U(VI) whereas La(III) and Ce(III) were found to have maximum sorption between pH 6.5–8.5. The elution studies were carried out with 0.01 M HCl for La(III) and Ce(III), 2.0 M HCl for Th(IV) and 0.25 M HCl for U(VI). The preconcentration factors for La(III), Ce(III), Th(IV) and U(VI) were 125, 130, 102 and 108, respectively. The resin shows good stability along with faster rate of equilibrium for all the metal ions. The influence of several ions (cations and anions) on the resin performance is also discussed. The relative standard deviation was between 96 and 98% with good analytical reliability. The proposed method was applied for the determination of metal ions in monazite sand and some standard geological materials.