Feasibility of using in situ fusion for the determination of Co,Cr and Mn in Portland cement by direct solid sampling graphite furnace atomic absorption spectrometry

In situ fusion on the boat-type graphite platform has been used as a sample pretreatment for the direct determination of Co, Cr and Mn in Portland cement by solid sampling graphite furnace atomic absorption spectrometry (SS-GF AAS). The 3-field Zeeman technique was adopted for background correction to decrease the sensitivity during measurements. This strategy allowed working with up to 200 µg of sample. The in situ fusion was accomplished using 10 µL of a flux mixture 4.0% m/v Na₂CO₃ + 4.0% m/v ZnO + 0.1% m/v Triton® X-100 added over the cement sample and heated at 800 °C for 20 s. The resulting mould was completely dissolved with 10 µL of 0.1% m/v HNO₃. Limits of detection were 0.11 µg g^− 1 for Co, 1.1 µg g^− 1 for Cr and 1.9 µg g^− 1 for Mn. The accuracy of the proposed method has been evaluated by the analysis of certified reference materials. The values found presented no statistically significant differences compared to the certified values (Student's t-test, p < 0.05). In general, the relative standard deviation was lower than 12% (n = 5).     

Effect of monomer molecular flow on electrode surface on the structure of poly(α-tetrathiophene) obtained by anodic polymerization

Different structures have been found for poly(α-tetrathiophene) [poly(α-4TF)] electrosynthesized on Pt by anodic oxidation of 1.0 mM monomer solutions in media such as 45:35:20 (v/v/v) acetonitrile/THF/DMF, 45:35:20 (v/v/v) acetonitrile/ethanol/DMF and 72:28 (v/v) acetonitrile/DMF containing 0.1 M LiClO₄; as well as 72:28 (v/v) acetonitrile/DMF with 0.1 M NaClO₃, under dynamic and static conditions at 25 °C. In all cases the polymer was generated by chronoamperometry at 1.000 V vs. Ag∣AgCl, corresponding to the first oxidation peak detected by cyclic voltammetry. Uniform, adherent, insoluble and black polymer films were obtained under these conditions. The resulting structures have been elucidated by combining the information of their IR spectrum, n_ox-value and doping level of the counterion. The degree of crosslinking of every polymer has been quantified and related to the molecular flow of monomer on the Pt electrode. A monomer concentration flow between 4 × 10⁻⁶ and 5 × 10⁻⁶ mmol cm⁻² s⁻¹ was determined as the limiting value below which the polymer grows with crosslinking. This value corresponds to the electropolymerization rate of α-4TF by Pt area unit at 25 °C.     

Development and validation of a hydrophilic interaction liquid chromatographic method for determination of aromatic amines in environmental water

A simple, precise, and accurate hydrophilic interaction liquid chromatographic (HILIC) method has been developed for the determination of five aromatic amines in environmental water samples. Chromatography was carried out on a bare silica column, using a mixture of acetonitrile and a buffer of NaH₂PO₄–H₃PO₄ (pH 1.5, containing 10 mM NaH₂PO₄) (85:15, v/v) as a mobile phase at a flow rate of 1 mL min⁻¹. Aromatic amines were detected by UV absorbance at 254 nm. The linear range of amines was good (r² > 0.998) and limit of detection (LOD) within 0.02–0.2 mg L⁻¹ (S/N = 3). The retention mechanism for the analytes under the optimum conditions was determined to be a combination of adsorption, partition and ionic interactions. The proposed method was applied to the environmental water samples. Aromatic amines were isolated from aqueous samples using solid-phase extraction (SPE) with Oasis HLB cartridges. Recoveries of greater than 75% with precision (RSD) less than 12% were obtained at amine concentrations of 5–50 μg L⁻¹ from 100 mL river water and influents from a wastewater treatment plant (WWTP). The present HILIC technique proved to be a viable method for the analysis of aromatic amines in the environmental water samples.     

Chiral separation of β-adrenergic blockers on CelluCoat column by HPLC

The chiral separation of 10 β-adrenergic blockers (acebutalol, alprenolol, bufuralol, bisoprolol, celiprolol, carazolol, indenolol, metoprolol, oxprenolol and propranolol) was achieved on CelluCoat column (250 mm × 4.6 mm, 5 μm particle size). The mobile phases used were (90:10:0.2, v/v/v) and (95:5:0.2, v/v/v) combinations of n-heptane-ethanol-diethylamine, respectively. The flow rates were 0.5, 1.0 and 2.0 mL min⁻¹ with detection at 225 nm. The capacity (k), selectivity (α) and resolution (R_s) factors were 0.44-12.91, 1.12-2.19 and 1.00-9.50, respectively. The proposed supra-molecular models indicated that the chiral resolution were governed by π-π interactions, hydrogen bondings and steric effect.     

Development and validation of a reversed-phase ion-pair high-performance liquid chromatographic method for the determination of risedronate in pharmaceutical preparations

A stability indicating, reversed-phase ion-pair high-performance liquid chromatographic method was developed and validated for the determination of risedronate in pharmaceutical dosage forms. The determination was performed on a BDS C₁₈ analytical column (250 mm × 4.6 mm i.d., 5 μm particle size); the mobile phase consisted of 0.005 M tetrabutylammonium hydroxide and 0.005 M pyrophosphate sodium (pH 7.0) mixed with acetonitrile in a ratio (78:22, v/v) and pumped at a flow rate 1.00 mL min⁻¹. The ultraviolet (UV) detector was operated at 262 nm. The retention times of magnesium ascorbyl phosphate, which was used as internal standard and risedronate were 4.94 and 5.95 min, respectively. The calibration graph was ranged from 2.50 to 20.00 μg mL⁻¹, while detection and quantitation limits were found to be 0.48 and 1.61 μg mL⁻¹, respectively. The intra- and inter-day percentage relative standard deviations, %R.S.D., were less than 5.9%, while the relative percentage error, %E_r, was less than 0.4%. The method was applied to the quality control of commercial tablets and content uniformity test and proved to be suitable for rapid and reliable quality control.     

Determination of clarithromycin in rat plasma by HPLC-UV method with pre-column derivatization

A novel high-performance liquid chromatographic (HPLC) method using pre-column derivatization and UV detection at 275 nm for the determination of clarithromycin in rat plasma has been validated. Clarithromycin was extracted from plasma sample spiked with internal standard (erythromycin) under alkaline condition with ethyl ether and derivatizated with trimethylbromosilane. The analyses were run on a C₁₈ column, maintained at 40 °C during elution, using a mobile phase comprised of potassium dihydrogen phosphate (50 mM, pH 6.8, contained 0.7% triethylamine), acetonitrile, and methanol (30:45:25, v/v/v). The standard calibration curve for clarithromycin was linear (r² = 0.9998) over the concentration range of 0.1-10 μg ml⁻¹ in rat plasma. The limit of detection (LOD) and limit of quantitation (LOQ) was 30 ng ml⁻¹ and 0.1 μg ml⁻¹ respectively. The intra- and inter-day assay variability range was 2.6-7.4% and 3.3-8.5%, respectively. This method has been successfully applied to a pharmacokinetic study of clarithromycin in rats.     

Comparison of direct solid sampling and slurry sampling for the determination of cadmium in wheat flour by electrothermal atomic absorption spectrometry

Two analytical methods for the determination of cadmium in wheat flour by electrothermal atomic absorption spectrometry without prior sample digestion have been compared: direct solid sampling analysis (SS) and slurry sampling (SlS). Besides the conventional modifier mixture of palladium and magnesium nitrates (10 μg Pd + 3 μg Mg), 0.05% (v/v) Triton X-100 has been added to improve the penetration of the modifier solution into the solid sample, and 0.1% H₂O₂ in order to promote an in situ digestion for SS. For SlS, 30 μg Pd, 12 μg Mg and 0.05% (v/v) Triton X-100 have been used as the modifier mixture. Under these conditions, and using a pyrolysis temperature of 800 °C, essentially no background absorption was observed with an atomization temperature of 1600 °C. About 2 mg of sample have been typically used for SS, although as much as 3-5 mg could have been introduced. In the case of SlS multiple injections had to be used to achieve the sensitivity required for this determination. Calibration against aqueous standards was feasible for both methods. The characteristic mass obtained with SS was 0.6 pg, and that with SlS was 1.0 pg. The limits of detection were 0.4 and 0.7 ng g⁻¹, the limits of quantification were 1.3 and 2.3 ng g⁻¹ and the relative standard deviation (n = 5) was 6-16% and 9-23% for SS and SlS, respectively. The accuracy was confirmed by the analysis of certified reference materials. The two methods were applied for the determination of cadmium in six wheat flour samples acquired in supermarkets of different Brazilian cities. The cadmium content varied between 8.9 ± 0.5 and 13 ± 2 ng g⁻¹ (n = 5). Direct SS gave results similar to those obtained with SlS using multi-injections; the values of both techniques showed no statistically significant difference at the 95% confidence level. Direct SS was finally adopted as the method of choice, due to its greater simplicity, the faster speed of analysis and the better figures of merit.     

Schiff bases as cadmium(II) selective ionophores in polymeric membrane electrodes

The construction and performance characteristics of polymeric membrane electrodes based on two neutral ionophores, N,N′-[bis(pyridin-2-yl)formylidene]butane-1,4-diamine (S₁) and N-(2-pyridinylmethylene)-1,2-benzenediamine (S₂) for quantification of cadmium ions, are described. The influences of membrane compositions on the potentiometric response of the electrodes have been found to substantially improve the performance characteristics. The best performance was obtained with the electrode having a membrane composition (w/w) of (S₁) (2.15%):PVC (32.2%):o-NPOE (64.5%):KTpClPB (1.07%). The proposed electrode exhibits Nernstian response in the concentration range of 7.9 × 10⁻⁸ to 1.0 × 10⁻¹ M Cd²⁺ with limit of detection 5.0 × 10⁻⁸ M, performs satisfactorily over wide pH range (2.0-8.0) with a fast response time (10 s). The sensor has been found to work satisfactorily in partially non-aqueous media up to 30% (v/v) content of methanol, ethanol and acetonitrile and could be used for a period of 2 months. The analytical usefulness of the proposed electrode has been evaluated by its application in the determination of cadmium in real samples. The practical utility of the membrane electrode has also been observed in the presence of surfactants.     

Spectrophotometric and spectrodensitometric determination of Clopidogrel Bisulfate with kinetic study of its alkaline degradation

Four sensitive, selective and precise stability-indicating methods for the determination of Clopidogrel Bisulfate (CLP) in presence of its alkaline degradate and in pharmaceutical formulations were developed and validated. Method A is a second derivative (D²) spectrophotometric one, which allows the determination of CLP in presence of its alkaline degradate at 219.6, 270.6, 274.2 and 278.4 nm (corresponding to zero-crossing of the degradate) over a concentration range of 4-37 μg mL⁻¹ with mean percentage recoveries 99.81 ± 0.893, 99.72 ± 0.668, 99.88 ± 0.526 and 100.46 ± 0.646, respectively. CLP can be determined in the presence of up to 65% of its degradate. D² method was used to study the kinetic of CLP alkaline degradation that was found to follow a first-order reaction. The t_1/2 was 6.42 h while K (reaction rate constant) was 0.1080 mol/h. Method B is the first derivative of the ratio spectra (DD¹) spectrophotometric method, by measuring the peak amplitude at 217.6 and 229.4 nm using acetonitrile and CLP can be determined in the presence of up to 70% of its degradate. The linearity range was 5-38 μg mL⁻¹ with mean percentage recoveries 99.88 ± 0.909 and 99.70 ± 0.952, respectively. Method C based on the determination of CLP by the bivariate calibration depending on simple mathematic algorithm which provides simplicity and rapidity. The method depends on quantitative evaluation of the absorbance at 210 and 225 nm over a concentration range 5-38 μg mL⁻¹ with mean percentage recovery 99.27 ± 1.115. CLP can be determined in the presence of up to 70% of its degradate. Method D is a TLC-densitometric one, where CLP was separated from its degradate on silica gel plates using hexane:methanol:ethyl acetate (8.7:1:0.3, v/v/v) as a developing system. This method depends on quantitative densitometric evaluation of thin layer chromatogram of CLP at 248 nm over a concentration range of 0.6-3 μg/band with mean percentage recovery 99.97 ± 1.161. CLP can be determined in the presence of up to 90% of its alkaline degradate. The selectivity of the proposed methods was checked using laboratory prepared mixtures. The proposed methods have been successfully applied to the analysis of CLP in pharmaceutical dosage forms without interference from other dosage form additives and the results were statistically compared with the official method.     

Ni(II) selective sensors based on Schiff bases membranes in poly(vinyl chloride)

The two nickel chelates of Schiff bases, 3-hydroxy-N-{2-[(3-hydroxy-N-phenylbutyrimidoyl)-amino]-phenyl}-N′-phenylbutyramidine (M₁) and bis-4-(ethyliminomethyl)naphthalene-1-ol (M₂), have been synthesized and explored as ionophores for preparing PVC-based membrane sensors selective to nickel ion. The influences of membrane compositions on the potentiometric response of the electrodes have been found to substantially improve the performance characteristics. The best performance was obtained with the electrode having a membrane composition (w/w; mg) of (M₁): PVC:NaTPB:CN in the ratio 5:150:5:150. The sensor shows a linear potential response for Ni²⁺ over a wide concentration range 1.6 × 10⁻⁷ to 1.0 × 10⁻² M with Nernstian compliance (30.0 ± 0.2 mV/decade of activity) within pH range 2.5-9.5 and a fast response time of 10 s. The sensor has been found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol, and acetonitrile and could be used for a period of 4 months. The analytical usefulness of the proposed electrode has been evaluated by its application in the determination of nickel in real samples. The practical utility of the membrane electrode has also been observed in the presence of surfactants.     

A highly selective mercury electrode based on a diamine donor ligand

(H₂NCHMeCH₂NH₂)(H₂O)₂HgCl₂ (I) was synthesised, characterised and used for the fabrication of a potentiometric sensor for Hg²⁺ metal ions. Membrane having I as electroactive material, sodium tetraphenyl borate (NaTPB) as an anion excluder, dibutylamine (DBA) as plasticizer in PVC matrix in the percentage ratio of 10:3:150:150 (I:NaTPB:DBA:PVC) (w/w) exhibits a linear response to Hg²⁺ ions in a concentration range of 1.25 × 10⁻⁵ to 1.0 × 10⁻¹ M having a detection limit of 8.9 × 10⁻⁶ with a slope of 25 ± 0.1 mV over the pH range 6.6-9.3. Selectivity coefficients for Hg(II) relative to a number of interfering ions were investigated. The electrode is highly selective for Hg²⁺ ions over a large number of mono-, bi-, and trivalent cations. Normal interferents like Ag⁺ and Cd²⁺ do not interfere in the working of the electrode. The electrode has also been used successfully in mixtures having a 10% (v/v) methanol and acetone content without showing any considerable change in working concentration range or slope. These electrodes have been found to be chemically inert showing a fast response time of 10 s and were used over a period of 4 months with good reproducibility (s = ±0.2). The electrode was used for determination of mercury in binary mixtures with 100% recovery and thus the proposed sensor can be used for real sample analysis.     

3-Iodoacetylaminobenzanthrone as a fluorescent derivatizing reagent for thiols in high-performance liquid chromatography

A new thiol-reactive derivatizing reagent, 3-iodoacetylaminobenzanthrone (IAB) has been developed for thiol analysis in liquid chromatography. In aqueous methanol containing 15 mM pH 8.3 H₃BO₃-KCl-Na₂CO₃ buffer, IAB reacted with thiols at 35 °C for 15 min. The derivatives of IAB with glutathione (GSH), cysteine (Cys), homocysteine (Hcy) and N-acetylcysteine (Nac) were well separated on a C₁₈ column with the mobile phase of methanol-water (50:50, v/v) containing 15 mM pH 2.7 H₃cit-Na₂HPO₄ buffer. At λ_ex/λ_em=420/540 nm, the detection limits were 20, 20, 55 and 40 fmol (1, 1, 2.3 and 2 nM), respectively, with a signal-to-noise ratio of 3. Owing to the preferential selectivity of iodoacetamidyl moiety to SH group, amino acids, aliphatic amines, phenol and alcohols had no obvious interference with the determination. The proposed method has been applied to the determination of thiols in human blood with recoveries of 98.5-105.3%.     

A simplified approach to the determination of N-nitroso glyphosate in technical glyphosate using HPLC with post-derivatization and colorimetric detection

A simple and sensitive HPLC post-derivatization method with colorimetric detection has been developed for the determination of N-nitroso glyphosate in samples of technical glyphosate. Separation of the analyte was accomplished using an anionic exchange resin (2.50 mm × 4.00 mm i.d., 15 μm particle size, functional group: quaternary ammonium salt) with Na₂SO₄ 0.0075 M (pH 11.5) (flow rate: 1.0 mL min⁻¹) as mobile phase. After separation, the eluate was derivatized with a colorimetric reagent containing sulfanilamide 0.3% (w/v), [N-(1-naphtil)ethilendiamine] 0.03% (w/v) and HCl 4.5 M in a thermostatized bath at 95 °C. Detection was performed at 546 nm. All stages of the analytical procedure were optimized taking into account the concept of analytical minimalism: less operation times and costs; lower sample, reagents and energy consumption and minimal waste. The limit of detection (k = 3) calculated for 10 blank replicates was 0.04 mg L⁻¹ (0.8 mg kg⁻¹) in the solid sample which is lower than the maximum tolerable accepted by the Food and Agriculture Organization of the United Nations.     

Validated stability-indicating densitometric thin-layer chromatography: application to stress degradation studies of minocycline

A simple, stability-indicating high-performance thin-layer liquid chromatographic (HPTLC) method for analysis of minocycline was developed and validated. The densitometric analysis was carried out at 345 nm using methanol-acetonitrile-isopropyl alcohol-water (5:4:0.5:0.5, v/v/v/v) as mobile phase.The method employed TLC aluminium plates pre-coated with silica gel 60F-254 as the stationary phase. To achieve good result, plates were sprayed with a 10% (w/v) solution of disodium ethylene diaminetetraacetic acid (EDTA), the pH of which was adjusted to 9.0. Compact spots of minocycline were found at R_f = 0.30 ± 0.02. For proposed procedure, linearity (r = 0.9997), limit of detection (3.7 ng spot⁻¹), recovery (99.23-100.16%), and precision (% R.S.D. ≤ 0.364) was found to be satisfactory. The drug undergoes acidic and basic degradation, oxidation and photodegradation. All the peaks of degradation products were well resolved from the pure drug with significantly different R_f values. The acidic and alkaline degradation kinetics of minocycline, evaluated using this method, is found to be of first order.     

Comparative study on 2-amino-1,4-naphthoquinone derived ligands as indium (III) selective PVC-based sensors

The three different ligands (Q₂ to Q₄) based on 2-amino-1,4-naphthoquinone (Q₁), have been synthesized and explored as neutral ionophores for preparing polyvinyl chloride-based membrane sensors selective to indium (III). The addition of potassium tetrakis(4-chlorophenyl) borate and various plasticizers, viz., o-NPOE, DBP, DBBP, DOP and CN has been found to substantially improve the performance of the sensors. The best performance was obtained with the sensor no. 16 having membrane of ligand (Q₂) with composition (%, w/w) ionophore Q₂ (3.0%):PVC (30.0%):o-NPOE (63.0%):KTpClPB (4.0%). This sensor exhibits Nernstian response with slope 19.8 mV/decade of activity in the concentration range 2.5 × 10⁻⁷ to 1.0 × 10⁻² M indium (III), performs satisfactorily over wide pH range of (2.5-7.5) with a fast response time (10 s). The sensor was also found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of acetonitrile, ethanol and methanol. The proposed sensor can be used over a period of 3.5 months without significant drift in potentials. The quantitative application of sensor was also evaluated by comparative analysis of artificially made sea water with AAS.     

Chromatographic fingerprints of industrial toluic acids established for their quality control

The chromatographic fingerprints of industrial o-toluic acid, m-toluic acid and p-toluic acid have been established by HPLC-UV detection according to their impurity groups. HPLC separation of all relative substances involved in the groups was developed on a Kromasil C₁₈ column by using methanol-water-NH₄Ac-HAc buffer (100 mM, pH 4.70) 15/65/20 (v/v/v) as the mobile phase at a flow rate of 1.5 mL/min, and detection was operated by UV adsorption at a wavelength of 254 nm. The ultraviolet spectra corresponding to each chromatographic peak were also recorded for further identification of all components. Whether the limits of relative impurities residues in a toluic acid product are qualified or not can be intuitively estimated by analyzing its chromatogram with comparison to the fingerprint. This protocol has successfully provided some Chinese manufacturers with a simple and feasible method for quality control of toluic acids for industrial use.     

Development of an HPLC method for the determination of mexiletine in human plasma and urine by solid-phase extraction

A sensitive and specific high-performance liquid chromatography (HPLC) method has been developed and validated for the quantification of mexiletine (MEX) in human plasma and urine. It uses solid-phase extraction (SPE) followed by an automated reversed-phase HPLC with a pre-column derivatization with 4-chloro-7-nitrobenzofurazan (NBD-CI) and UV-vis Absorbance detection. The process was set as: the UV-vis Absorbance wavelength was set at 458 nm. Chromatographic separation was performed on a Phenomenex-C₁₈ Column (Aqua, 150 mm × 4.6 mm i.d. with 5 μm particle size) with the mobile phase consisting of acetonitrile and water (80:20, v/v), and the flow rate was set at 1.0 mL min⁻¹. Calibration of the overall analytical procedure gave a linear signal (r > 0.9998) over a MEX concentration range of 0.2-2.0 μg mL⁻¹ in human plasma and urine. The detection limit in plasma and urine was 0.1 μg mL⁻¹. Intra- and inter-day precision of the assay at three concentrations within this range were 0.31-2.50%. The high specificity and sensitivity have been achieved by this fast method (total run-time <6 min). The method has been successfully validated in human plasma and urine and it has been shown to be precise, accurate and reliable.     

Preconcentration and determination of boron in milk,infant formula,and honey samples by solid phase extraction-electrothermal atomic absorption spectrometry

This work presents alternative procedures for the electrothermal atomic absorption spectrometric determination of boron in milk, infant formulas, and honey samples. Honey samples (10% m/v) were diluted in a medium containing 1% v/v HNO₃ and 50% v/v H₂O₂ and introduced in the atomizer. A mixture of 20 µg Pd and 0.5 µg Mg was used for chemical modification. Calibration was carried out using aqueous solutions prepared in the same medium, in the presence of 10% m/v sucrose. The detection limit was 2 µg g^− 1, equivalent to three times the standard error of the estimate (s_y/x) of the regression line. For both infant formulas and milk samples, due to their very low boron content, we used a procedure based on preconcentration by solid phase extraction (Amberlite IRA 743), followed by elution with 2 mol L^− 1 hydrochloric acid. Detection limits were 0.03 µg g^− 1 for 4% m/v honey, 0.04 µg g^− 1 for 5% m/v infant formula and 0.08 µg mL^− 1 for 15% v/v cow milk. We confirmed the accuracy of the procedure by comparing the obtained results with those found via a comparable independent procedure, as well by the analysis of four certified reference materials.     

Comparative studies of ONNO-based ligands as ionophores for palladium ion-selective membrane sensors

Palladium sensors based on two neutral ionophores, N,N′-bis(acetylacetone) cyclohexanediamine (L₁) and N,N′-bis(o-hydroxyacetophenone)-1,2-cyclohexanediamine (L₂) for quantification of palladium ions are described. Effect of various plasticizers (o-NPOE, DBP, DEP, DOP, TBP, and CN) and anion excluder, sodium tetra phenyl borate (NaTPB) has been studied. The best performance is obtained with a membrane composition of PVC:o-NPOE:ionophore (L₁):NaTPB of 150:300:5:5 (%, w/w). The sensor exhibits significantly enhanced selectivity towards palladium ion over the concentration range 1.0 × 10⁻⁸ to 1.0 × 10⁻¹ M with a lower detection limit of 4.0 × 10⁻⁹ M and a Nernstian compliance (29.1 ± 0.3 mV decade⁻¹ of activity) within pH range 2.0-6.0 and fast response time of 10 s. Influence of the membrane composition and possible interfering ions has also been investigated on the response properties of the electrode. Fast and stable response, good reproducibility and long-term stability of the sensor are demonstrated. The sensor has been found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol and acetonitrile and could be used for a period of 4 months. Selectivity coefficients determined with fixed interference method (FIM) indicate high selectivity for palladium. The proposed electrode shows fairly good discrimination of palladium from other cations. The application of prepared sensor has been demonstrated in determination of palladium ions in spiked water sample.     

Temperature-induced inversion of elution order in the chromatographic enantioseparation of 1,1′-bi-2-naphthol on an immobilized polysaccharide-based chiral stationary phase

In this work, the enantioseparations of 1,1′-bi-2-naphthol (BINOL) and its three derivatives were performed on an immobilized polysaccharide-based chiral stationary phase, Chiralpak IA, under normal-phase mode. The effects of the content of polar modifier in the mobile phase and the column temperature on the retention and enantioseparation were investigated in detail. Temperature-induced inversion of elution order for BINOL was observed directly when n-hexane/2-propanol (92/8, v/v) was used as mobile phase. The isoenantioselective temperature (T_iso) was calculated to be 31.4 °C. When n-hexane/2-propanol/THF (93/2/5, v/v/v) was used as mobile phase, the T_iso value decreased to −8.2 °C. Entropically driven enantioseparation which had practical application was obtained successfully (separation factor being 1.189 and 1.332 at 25 °C and 50 °C, respectively). The corresponding thermodynamic parameters for other three binaphthyl compounds were compared with that for BINOL. Some inferences about chiral recognition mechanism were stressed.