1. Table 3. Summary of chromatographic procedures found in literature survey for the determination of Tamsulosin HCl in different matrices Alankar Shrivastava et al. Various Analytical Methodologies for Determination of Selective α1A Receptor Blocker Tamsulosin Hydrochloride and Its Combinations in Different Matrices. World Journal of Analytical Chemistry, 2013, Vol. 1, No. 3, 37-48. doi:10.12691/wjac-1-3-3 © The Author(s) 2013. Published by Science and Education Publishing. MethodChromatographic conditionLinear rangeLODLOQApplicationReference LC-MS/MSBonchrom XBP-C 18 column using a mobile phase consisted of methanol-acetonitrile-ammonium formate (10mmol x L -1 ) (30 : 40 :30, v/v/v), at a flow rate of 0.4 mL x min -1 0.02 - 50ng/mlNM0.02 ng/mlIn dog plasma after oral administration of controlled-release tablet[44] LC–MS–MSJ’sphere ODS-80H column (75mm×34.6mm I.D., 5μm, YMC, Tokyo, Japan). Mobile phase: 50mM acetic acid adjusted to pH 4.0 with 50mM ammonium acetate and methanol (4:6 v/v). Column temperature: 40°C. Flow-rate: 0.5ml/min10–1000pg/ml in plasma dialysate, 0.5–50ng/ml in plasma, and 1–100ng/ml in urineNM In human plasma dialysate, plasma and urine[45] LC–ESI-MSC 18 reversed-phase column using a mobile phase of methanol–water–acetic acid–triethylamine (620:380:1.5:1.5, v/v).0.2–30ng/mlNM0.1ng/mlPharmacokinetics in adult humans[46] HPLC-UVChiralcel OD-RH column (250mm × 4.6mm, Daicel Chemical Industaies.Ltd, Japan) packed with 5μm silica gel coated by Cellulose tris(3,5-dimethylphenylcarbamate)with a binary solvent mixture of 50 mmol l −1 KPF 6 –acetonitrile (v/v (70:30), pH 5.0). Flow rate: 1 ml/min. Wavelength 225 nm. Column temperature 25-30°C. 0.03–6.0 μgml −1 for R-isomer and 0.028–5.6 μgml −1 for S-isomer 0.11 for both R & S resp0.44ng for both R & S respSeparation of tamsulosin and its S-isomer[47] HPLC-FOctadecylsilica column (55mm × 4mm, 3μm particles). Mobile phase: acetonitrile–30mM dihydrogenpotassium phosphate (25:75 v/v). 228/326nm (excitation/emission wavelength).0.397–40.50ng/mlNM0.4ng/ml using 1ml of plasmaIn human plasma[48] LC-TMSZorbax Extend-C 18 column (150mm × 4.6mm i.d., 5μm, Agilent, Palo Alto, CA, USA) with a SecurityGuard C 18 guard column (4mm×3.0mm i.d., Phenomenex, Torrance, CA, USA). Mobile phase: Methanol, water and formic acid (80:20:1, v/v/v) was delivered at a flow rate of 0.5ml/min. Column temperature 20°C.0.1–50.0ng/ml-0.1ng/mlDog plasma[49] LC–MS/MS Waters XTerra C 8 column (50mm×2.1mm, 3.5μm, Waters, Milford, MA, USA) and a Zorbax XDB-C 8 Narrow-Bore Guard Column (Agilent Technologies, Palo Alto, CA, USA). The mobile phase consisted of water–formic acid (A; 100:0.1, v/v) and water–acetonitrile–formic acid (B; 50:50:0.1, v/v/v). The gradient programwas as follows: 0–5min: 10% B→100% B; 5–6 min: 100% B→10% B; 6–8 min: 10% B→10% B. Column temperature 30°C. 0.1–4.7ng/ml and 0.1–19.3ng/ml for aqueous humor and serum samples resp.NM0.1 ng/ml for both human aqueous humor and serum samplesHuman aqueous humor and serum[50] RP-LC/ESI-MS–MS* Hypersil BDS C 18 (250mm×4.6 mm) 5μm (Thermo Electron Corporation, Runcorn, UK). Inertsil ODS 3v (250mm×4.6mm) 5μm (G.L. Sciences, Tokyo, Japan). XTerra C 18 (250mm×4.6mm) 5μm (Waters, Milford, MA, USA). Kromasil KR100-5C 18 (250mm×4.6mm) 5μm (Eka Chemicals, Bohus, Sweden). Symmetry C 18 (250mm×4.6mm) 5μm (Waters, Milford, MA, USA). Mobile phase was 10mM ammonium acetate– acetonitrile in a gradient elution mode of a flow rate of 1.0ml/min at 30°C. Photodiode array detector 280nm 0.5 to 5.0μg/ml0.06–0.11μg/ml0.21-0.39 μg/mlBulk drugs and formulations[51] HPLC-UVLichrosphere ODS C 8 RP Column (4.6mm ID, 250mm L, particle size 5 Micron, at wavelength of 280nm. Mobile phase (Potassium Dihydrogen Orthophosphate and Acetonitrile) at the flow rate of 1.2ml/min. λ = 280nmNM Analysis in bulk drugs[52] HPTLCAluminium plates pre-coated with silica gel 60F 254 as the stationary phase and the mobile phase consisted of acetonitrile/methanol/dichloromethane (2.0: 1.0: 2.0, v/v/v)300–800ng8.49ng per 25.72ng per band Tablets[53] HPLC-UVInertsil ODS 3V (5 μ, 15 x 4.6mm) column, in an isocratic mode, using acetonitrile:buffer (30 : 70) as mobile phase. pH 3 adjusted with perchloric acid. Flow rate 2 mL/minute and elution monitored at 220 nm.100 to 500μg/mlNM Pellets 0.2%[54] HPLC-UVODS, Phenomonex,C 18 (250x4.6 mm, 5μ) column using a mobile phase consisting of sodium dihydrogen orthophosphate buffer-Acetonitrile (70:30).The eluent was monitored at 280nm.NM bulk and tablet[55] HPTLC Aluminium plates pre-coated with silica gel 60F-254 as stationary phase. The solvent system consisted of toluene-methanol-triethylamine 9:3:1 (v/v/v). 200–3000ng10ng50ngbulk and tablets[56] HPLC-UVC 18 column using gradient LC method, solution A: aqueous ortho phosphate buffer pH 6.5 and B: mixture of water: acetronitrile (90:10%v/v). The method was linear over a range of 0.2 to 1.9μg/ml. λ = 286nm0.2 to 1.9μg/ml0.007μg/ml0.020μg/mlintermediates in the reaction mixtures and the finished products[57] HPLC-UVSupelcosil LC-18 column (25cm×4.6mm; 5 mm particle size) preceded by a Sentry guard column. Mobile phase: acetonitrile 70% (pH 3.4 adjusted with glacial acetic acid), flow rate of 0.75mL/min. Photodiode array detector at 225nm.0.025–1.00mcg/mL.0.015μg/ml0.025μg/mldissolution study of OMNIC ® capsules[58] HPTLCAluminium plates precoated with silica gel 60 F-254 as the stationary phase while the solvent system consisted of toluene : methanol : triethylamine (3.5 : 1.2 : 0.2v/v). Absorbance mode at 280 nm.400–2400 ng per spot20.49 ng per spot62.10 ng per spotBulk and tablets[59] HPLC-UVODS C 18 Column 250 X 4.6 mm (particle size of 5μ), Mobile phase: acetonitrile: (0.05M) KH 2 PO 4 buffer (45:55) at flow rate 1.8ml/min, monitored at 240nm.10-50μg/ml0.495μg/ml0.461μg/mlBulk and tablets[60] HPLC-UVMicrobondapak C18 (Lichrospher, Darmstadt, Germany) column of 250mm × 4.6mm i.d. particle size of 5μm. C 18 column with a simple isocratic mobile phase consisting methanol: 50mM phosphate buffer (pH 7.8, ratio 80:20) at a flow rate of 1 ml/m. λ = 230nm5-250μg/ml10ng/ml50ng/mltablets[61] HPLC-UVChiral separations were performed using 4.6×250mm,5μm, columns: Chiralcel OD-H (cellulosetris (3,5-dimethylphenylcarbamate)) and Chiral pakAD-H (amylosetris (3,5-dimethylphenyl carbamate)) from Daicel Chemical Industries Ltd. Mobile phase: hexane–isopropylalcohol– triethylamine (80:20:0.2, v/v/v), flowrate 1.2 ml/min, detection UV 279nm, t = 25°C.1–100μg/ml0.2μg/ml [both isomers]0.6μg/ml [both isomers]Enantioseparation & determination of(R,S)-isomers in tablet and capsules formulations[62] LC–MS/MSLuna C 18 column (2.0mm × 50mm, 5μm particles) with a mobile phase of 10 mM ammonium formate buffer (pH 3.5)–methanol (25:75, v/v) and quantified by MS/MS detection in ESI positive ion mode. The flow rate of the mobile phase was 200 μL/min. t = 30°C0.01–20ng/mL0.01ng/mL-Pharmacokinetic study in humans.[63] HPLC-UVLichrocart / Lichrosphere C 18 column (250 x 4.0mm packed with 5 μ) with mobile phase consisting of a mixture of Acetonitrile: T.D.W. in the ratio (40: 60). Flow rate was 0.8 mL / min. Detection at 275nm.1-200μg/mL0.36μg/mL0.74μg/mLtablets[64] HPLC-UVInertsil ODS 3V (5 microns,15cm x 4.6mm).Mixture of 100 ml Perchloric acid solution + 565ml water. Adjust pH=2.0 with 1N sodium hydroxide solution or with perchloric acid solution. Diluted with water to 700ml and added 300ml acetonitrile. λ = 220nm.100-500μg/ml.NM pellets[65] HPLC-UVC 18 column with a mobile phase consisting of acetonitrile and water in the ratio of 50:50 v/v. The mobile phase was pumped at a flow rate of 1.5ml/min. The eluents were monitored at 214nm5 to 100μg/ml0.019μg/ml0.0575μg/mltablets[66] LC-MSNucleosil C 18, 5 μm (125 mm x 4.0 mm i.d.) column with oven temperature at 40°C. Mobile phase consisted of methanol and 0.05M ammonium acetate buffer pH 3.7 (6:4, v/v, flow rate v/v, flow rate at 0.5mL/min)0.7-35ng/ml0.1ng/mL0.7ng/mLbioavailability studies[67] HPLC-UVDissolve 3.0g of sodium hydroxide in a mixture of 8.7mL of perchloric acid and 1.9L of water; adjust to pH 2.0 with 0.5M sodium hydroxide and dilute to 2L with water; to 1.4L of this solution, add 600mL of acetonitrile. ODS column, (150×4.6mm), 5μ particle size. t = 40°C. Flow rate 1.3ml/min, λ = 225nm.NM Related substances [19] HPLC-UVColumn 250×4.6mm, Silica gel for chiral separation, Mobile phase diethylamine, methanol, anhydrous ethanol, hexane (1:150:200:650 V/V/V/V). Flow rate 0.5mL/min. Detection Spectrophotometer at 225nm. t = 40°C.NM Enantiomeric purity HPLC-UV A stainless steel column 4 mm in inside diameter and 15cm in length, packed with octadecylsilanized silica gel for liquid chromatography (5mm in particle diameter). t = 40°C. Mobile phase: Dissolve 4.4mL of perchloric acid and 1.5g of sodium hydroxide in 950mL of water, adjust the pH to 2.0 with sodium hydroxide, and add water to make 1000 mL. To 700mL of this solution add 300mL of acetonitrile. Adjust the flow rate so that the retention time of tamsulosin is about 6 minutes. (wavelength: 225nm) NM Related substances[17] LC-MSNucleosil C 18, 5μm (125mm x 4.0mm i.d., Phenomenex, USA) column with oven temperature of 40°C. The mobile phase consisted of methanol and 0.05M ammonium acetate buffer pH 3.7 (6 : 4, v/v) and the flow rate was 0.5μL/min.0.7-35.0 ng/ml 0.1 ng/mL 0.7ng/mLPharmacokinetics study[68] HPLC-UVInertsil ODS 3V, 150mm × 4.6mm × 5μm or its equivalent in isocratic mode, with mobile phase compressing of Buffer: Acetonitrile(70:30) The flow rate was 1.5ml/min and the detection was carried out by PDA detector i.e., 225nm80 to 120μg/mL0.1920 μg/mL0.5813μg/mLPellets[69] HPLC-UVAce 5-C 18 (250×4.6mm, 5μm) column, and 10 mmol L -1 methanol and water (70:30 v/v) as a mobile phase. The detection was at the wavelength of 280 nm. Flow rate 1ml/min.2-30μg/ml0.24 μg/ml0.73μg/mlBulk and tablets[70] LC-MSWaters symmetry C 18 column with a mobile phase of 0.03% formic acid–acetonitrile (30:70, v/v)0.1–50.0ngNM100pg/mlPharmacokinetic, bioavailability or bioequivalence studies[71] HPLC-UV ODS (150mm×4.6mm,5μm ） Column, using methanol-0.2mmol·L-1 Na2HPO4-KH2PO4 （ pH 5.9 ） （ 6:4 ） as the mobile phase. The flow rate was 1.0mL·min-1,the detection was set at 275nm and the column temperature was maintained at 30°C. NM Yankening and Yujin Yinxie tablets.[72] HPLC-UVODS (150mm ×4.6mm,5μm) column,using methanol-0.2 mmol/L -1 Na 2 HPO 4 -KH 2 PO 4 (pH 5.9)(6:4) as the mobile phase. The flow rate was 1.0mL/min -1, the detection wavelength was set at 275nm and the column temperature was 30°C.5.06-130.65μg/mLNM Capsules and related substances[73] UPLC–MS–MSAcquity UPLC Beh C 18, 2.1 × 50mm, 1.7 µm, Mobile phases: A: 0.1% HCOOH in water B: MeOH, Gradient: 95% A to 25% A in 1 min, hold 0.5 min, ramp to 2% A in 0.1 min and hold for 0.4 min return to initial (2.5 min total cycle time), Flow-rate: 0.6 mL/min, Temperature: 35°C0.01 to 10ng/mL.NM0.01ng/mLTamsulosin (Flomax) in Human Plasma[74] HPLC-UVChiralcel OD-R column (250×4.6, 10μ). Mobile phase: mixture of 0.5mol/L sodium perchlorate and acetonitrile (80:20, v/v, pH 4.0). Flow rate 0.4 ml/min, detection 223nm.NM Enantiomers and synthetic intermediates of drug[75] HPLC-UVChiralpak AD-H column (250 ×4.6mm, 5μ, Daicel make). Mobile phase: hexane:isopropanol:methanol (65:15:25, v/v/v). Wavelength: 225nm0.5-3.0mg/ml150ng/ml50ng/mlEnantiomers separation[76] HPLC-UVZorbax SB-CN 250×4.6mm, 5μ column. Mobile phase: 10 mM ammonium acetate-ACN (40:60, v/v). wavelength 225nm. Flow rate 1 ml/min25-150μg/mLNM Separation of impurities and drug[77] NM: Not mentioned