High Performance Liquid Chromatographic Methods

Although GLC methods have undoubtedity been useful the most effective analysis for both technical and natural CNSL has teen by HPLC (refs. 219,220) which has the advantage that no derivatisation is required and further, that peaks for formerly unobserved oligomeric materials can now be obtained. By the use of an internal standard the non-volatile polymeric material in technical and in natural cashew nut-shell liquid can also be determined and a total analysis of these products obtained. 

With the aid of gradient elution, a reversed phase partition method and an internal standard, considerable progress has been made in the quantitative determination of each constituent of the main component phenols present in technical CNSL and in natural cashew-nut shell liquid provided that relative molar response (RMR) factors are used. A typical quantitative HPLC analysis of the technical material indicated cardanol (67.8%), cardol (18.2%), 2-methylcardol (3.3%), minor constituents (3.3%) and polymeric material (7.4%). 

The % distribution of the unsaturated constituents of cardanol and cardol by HPLC analysis is shown in Table 6. 

TABLE 13.7 %COMPOSmON of NATURAL CNSL by DIFFERENT CHROMATOGRAPHIC TECHNIQUES  

METHOD ANACARDIC ACID CARDOL 2-METHYLCARDOL CARDANOL 

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High-Performance Liquid Chromatographic Method Applied to Parafytic Shellfish Poisoning Research... 

MAiANi G, SERAFiNi M, SALUCCi M, AZZiNi E and FERRO-Luzzi A (1997) Application of a new high-performance liquid chromatographic method for measuring selected polyphenols in hiunan plasma , J of Chromatog B, 692, 311-17. 

Snyder, L. R., Dolan, J. W. Initial experiments in high-performance liquid chromatographic method development. I. Use of a starting gradient run. J. Chromatogr. A 1996, 721, 3-14. 

Marvin, C. H., Brindle, I. D., Singh, R. P., Hall, C. D., and Chiba, M., Simultaneous determination of trace concentrations of benomyl, carbendazim (MBC) and nine other pesticides in water using an automated on-line pre-concentration high-performance liquid chromatographic method, /. Chromatogr., 518, 242, 1990. 

Virtanen, V. and Lajunen, L. H. J., High-performance liquid chromatographic method for simultaneous determination of clodronate and some clodronate esters, /. Chromatogr., 617, 291, 1993. 

N. A. Parris, Instrumental Liquid Chromatography, a Practical Manual on High-Performance Liquid Chromatographic Methods (Journal of Chromatography Library, Vol. 27), Elsevier, Amsterdam, 2nd revised ed., 1984 J. Drozd, Chemical Derivatization in Gas Chromatography (Journal of Chromatography Library, Vol. 19), Elsevier, Amsterdam, 1981 J. F. Lawrence and... 

Kurttio, P, Vartianen, T., and Savolainen, K. (1988) High-performance liquid chromatographic method for the determination of ethylenthiourea in urine and on filters, Analytical Chemistry Acta, 212 297-301. 

Schleyer, E., Reinhardt, J., Unterhalt, M., Hiddemann, W. (1995). Highly sensitive coupled-column high-performance liquid chromatographic method for the separation and quantitation of the diastereomers of leucovorin and 5-methyltetrahydrofolate in serum and urine. J. Chromatogr. B 669, 319-330. 

Soltes, L., Sebille, B. (1997). Reversible binding interactions between the tryptophan enantiomers and albumins of different animal species as determined by novel high performance liquid chromatographic methods an attempt to localize the d- and L-tryptophan binding sites on the human serum albumin polypeptide chain by using protein fragments. Chirality 9, 373-379. 

Erk and Altun [24] used a ratio spectra derivative spectrophotometric method and a high performance liquid chromatographic method for the analysis of miconazole nitrate and metronidazole in ovules. The spectral method depends on ratio spectra first derivative spectrophotometry, by utilizing the linear relationship between substances concentration and ratio spectra first derivative peak amplitude. The ratio... 

Sternson et al. [58] used a high performance liquid chromatographic method for the analysis of miconazole in plasma. Miconazole was extracted from alkalinized plasma with n-heptane-isamyl alcohol (98.5 1.5) and separated by high performance performance liquid chromatography on p-Bondapak Ci8 with ultraviolet detection at 254 nm. The mobile phase was methanol-tetrahydrofuran-acetate buffer (pH 5) (62.5 5 32.5) containing 5 mmol octanesulfonate per liter. The flow rate was 2 mL/min. Recovery was 100%. The relative standard deviation for injection-to-injection reproducibility was 0.4% and that for sample-to-sample variation was 5% at high miconazole concentrations (30 pg/mL) and 1% at low (1 pg/mL) concentrations. The limit of detection was 250 ng/mL. 

Fan used a high performance liquid chromatographic method for the qualitative and quantitative analysis of miconazole [59], Miconazole sample was dissolved in methanol and determined by high performance liquid chromatography using methanol-water (75 25) as the mobile phase and ultraviolet detection at 214 nm, the recovery was more than 99.4% and the accuracy was satisfactory for the qualitative and quantitative analysis. 

Guillaume et al. [69] presented a high performance liquid chromatographic method for an association study of miconazole and other imidazole derivatives in surfactant micellar using a hydrophilic reagent, Montanox DF 80. The thermodynamic results obtained showed that imidazole association in the surfactant micelles was effective over a concentration of surfactant equal to 0.4 pM. In addition, an enthalpy-entropy compensation study revealed that the type of interaction between the solute and the RP-18 stationary phase was independent of the molecular structure. The thermodynamic variations observed were considered the result of equilibrium displacement between the solute and free ethanol (respectively free surfactant) and its clusters (respective to micelles) created in the mobile phase. 

Gagliardi et al. [72] developed a simple high performance liquid chromatographic method for the determination of miconazole and other antimycotics in cosmetic antidandruff formulations. This high performance liquid chromatographic method was carried out on a Discovery RP Amide Ci6 column and spectrophotometric detection was performed at 220 nm. The initial mobile phase was a mixture of acetonitrile and aqueous 0.001 M sodium perchlorate (pH 3) in the ratio of 15 85 (v/ v) then a linear gradient less than 46% acetonitrile in 70 min, and less than 50% in 80 min. The extraction procedure was validated by analyzing samples of shampoo... 

Hasegawa et al. [76] measured miconazole serum concentration by a high performance liquid chromatographic method. The authors assessed whether the internal standard method produced an intra-assay error and found that the method gave more precise and more reproducible results compared to the absorption calibration curve method. With 0.5 pg/mL of miconazole, the coefficient of variation produced by that method was 3.41%, whereas that of the absorption calibration curve method was 5.20%. The concentration of absorptions calibration curve method showed higher values than the internal standard method. This indicated that the internal standard method was far more precise in measuring the miconazole serum concentrations than the absorption calibration curve method. 

Table 6 summarizes the conditions of the other high performance liquid chromatographic methods, which are reported in the literature for the separation and analysis of miconazole in bulk, pharmaceutical formulation, and biological fluids [60, 83-91]. 

Parkhurst et al. [79] described a high performance liquid chromatographic method for the simultaneous determination of primaquine and its metabolites from plasma and urine samples, utilizing acetonitrile deproteinization, and direct injection onto a cyano column. Levels of 100 ng/mL per 20 pL injection could be quantitated. Preliminary pharmacokinetic analysis is reported for two human subjects after oral doses of 60 90 mg primaquine diphosphate. Two apparent plasma metabolites and two possible urinary metabolites are also reported. 

Katori et al [84] used a high performance liquid chromatographic method for the determination of primaquine phosphate tablets. Chromatography on a TSK Gel-4 (octadecylsilanized) column was used to determine the active ingredient in tablets and injections for treating tropical diseases. The mobile phase used is 26% acetonitrile in 0.05-M pH-3 phosphate buffer and the drug was detected at 260 nm. The peak area and peak height reproducibilities were <1.69%, and results compared well with those of other methods. 

Sidhu et al [86] developed a reliable and simple high performance liquid chromatographic method for the routine analysis of pharmaceutical dosage forms using a Cig Bondapak reversed-phase column with a binary solvent system consisting of... 

Rao et al. [87] developed a high performance liquid chromatographic method for the determination of primaquine phosphate in pharmaceutical dosage form. A /(-Bondapak NH2 column with chloroform-methanol (60 40) as eluent was selected with sulfalene as internal standard. The method was convenient with recovery of approximately 100% for primaquine. 

Dean et al. [93] used a high performance liquid chromatographic method for the simultaneous determination of primaquine and carboxyprimaquine in plasma with electrochemical detection. After the addition of the internal standard, plasma was deproteinized by the addition of acetonitrile. Nitrogen-dried supernatants, resuspended in mobile phase were analyzed on a C8 reversed-phase column. Limits of detection for primaquine and carboxyprimaquine were 2 and 5 ng/mL with quantitation limits of 5 and 20 ng/mL, respectively. The assay sensitivity and specificity are sufficient to permit quantitation of the drug in plasma for pharmacokinetics following low dose (30 mg, base) oral administration of primaquine, typically used in the treatment of malaria and P. carinii pneumonia. 

P. Lozano, M.R. Castellar, M.J. Simancas and J.L. Iborra, Quantitative high performance liquid chromatographic method to analyse commercial saffron (Crocus sativus L.) products, J. Chromatogr., A, 830, All 483 (1999). 

Garst, J.E. (1984) Accurate, wide range, automated, high performance liquid chromatographic method for the estimation of octanol/water partition coefficients. II Equilibration in partition coefficient measurements, additivity of substituent-constants and correlation of biological data. J. Pharm. Sci. 73(11), 1623-1629. 

A coupled enzymic high-performance liquid chromatographic method has been used to determine down to 0.1-0.8 xM of formate in sea water [130]. 

Tsuji and Goetz24 developed a quantitative high performance liquid chromatographic method for separating and measuring erythromycins A, B, and C, their epimers and degradation products. This method uses a /iBondapak Ci 8 reverse column with acetonitrile-methanol-O.2m ammonium acetate-water (45 10 10 25) as solvent. The pH and composition of the mobile phase may be adjusted to optimize resolution and elution volume. The authors utilized the procedure on USP reference standard and report a relative standard deviation of 0.64%. 

A high-performance liquid chromatographic method for nalidixic acid on a strong anion-exchange resin column has been reported, using a mobile phase of 0.01 M sodium tetraborate at pH 9.2 and 0.003 M sodium sulfate. The relative retention time for nalidixic acid in the system reported by Sondach and Koch was 0.86 with sulfanilic acid as the standard at... 

Andersen, A., Warren, D J., and Slordal, L. 1993. A sensitive and simple high performance liquid chromatographic method for the determination of doxorubicin and its metabolites in plasma. Ther Drug Monit. 15 455. 

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