Sol–gel synthesis of Na<Subscript>2</Subscript>CaSiO<Subscript>4</Subscript> and its in vitro biological behaviors

In this work we prepared the hybrid material (SG) by the sol–gel method through the reaction between tetraethylortosilicate (TEOS) and acetylacetonatepropyltrimethoxysilane (ACACSIL). We also immobilized the acetylacetonate on silica surface (GR) by the grafting method through the reaction between a commercial silica and ACACSIL. Infrared thermal analysis showed that these materials were thermally stable until 200 °C. SG is a microporous material and has surface area of 500 m² g⁻¹, average porous volume of 0.09 cm³ g⁻¹ and organic content of 1 mmol g⁻¹. GR is a mesoporous material and has surface area of 300 m² g⁻¹, average porous volume of 0.7 cm³ g⁻¹ and organic content of 0.4 mmol g⁻¹. Iron(III) was coordinated to SG and GR resulting in the SG–Fe and GR–Fe silicas which were tested as catalysts on the aerobic epoxidation of cis-cyclooctene. SG–Fe yielded 100% of conversion and 94% of selectivity in epoxide whereas GR–Fe silica led to a maximum conversion of 50% and 100% of selectivity.     

Catanionic surfactant ambient cloud point extraction and high-performance liquid chromatography for simultaneous analysis of organophosphorus pesticide residues in water and fruit juice samples

A mixed anionic–cationic surfactant cloud point extraction (CPE) has been developed using sodium dodecyl sulfate (SDS) and tetrabutylammonium bromide (TBABr) for the extraction and preconcentration of organophosphorus pesticides (OPPs) at ambient temperature before analysis by high-performance liquid chromatography. The studied OPPs were azinphos-methyl, parathion-methyl, fenitrothion, diazinon, chlorpyrifos, and prothiophos. The optimum conditions of the mixed anionic–cationic CPE were 50 mmol L⁻¹ SDS, 100 mmol L⁻¹ TBABr, and 10% (w/v) NaCl. The extracted OPPs were successfully separated within 11 min using the conditions of a Waters Symmetry C8 column, a flow rate of 0.8 mL min⁻¹, a gradient elution of methanol and water, and detection at 210 nm. Linearity was found over the range 0.05–5 μg mL⁻¹, with the correlation coefficients higher than 0.996. The enrichment factor of the target analytes was in the range 6–11, which corresponds to their limits of detection from 1 to 30 ng mL⁻¹. High precisions (intra-day and inter-day) were obtained with relative standard deviation <1.5% (t _R) and 10% (peak area). Accuracies (% recovery) of the different spiked OPP concentrations were 82.7–109.1% (water samples) and 80.3–113.3% (fruit juice samples). No contamination by the OPPs was observed in any studied samples.     

Preparation of Novel Materials for Catalysts Utilizing Metal-Containing Silsesquioxanes

Recent progress of the preparation of novel materials for catalysts utilizing metal-containing silsesquioxanes are reviewed in the following categories: (i) activities of vanadium or titanium-containing silsesquioxanes as homogeneous catalysts for oxidative reactions, (ii) preparation of immobilized or polymeric catalysts, and (iii) preparation of porous oxide catalysts utilizing metal-containing silsesquioxanes. The present authors found that the liquid phase photo-oxidation of cyclohexane in the presence of a vanadium-containing silsesquioxane as a homogeneous catalyst selectively afforded cyclohexanol and cyclohexanone in high yields. Facile synthetic methods for group 4 metal-containing silsesquioxanes with functionalized silyl (or germyl) groups are presented. Remarkably, titanocene(IV)-containing silsesquioxanes have been synthesized for the first time. The presence of alkenylsilyl substituents shows a promotional effect on the epoxidation of cycloalkenes, which was found to be more significant for titanium-bridged silsesquioxanes. By utilizing these silsesquioxanes, polymeric, starburst-like, and dendritic silsesquioxanes were prepared as well as novel caged or macrocyclic molecules with organic–inorganic hybrid structures. The controlled calcination of these metal-containing silsesquioxanes at around 823 K produces porous oxides with high BET surface areas of 300–520 m²g⁻¹ and uniformly-controlled micropores of 0.5–0.6 nm diameter. The oxides are found to include a well-dispersed metallic oxide species. From group 13 elements-containing silsesquioxanes Br?nsted acidic oxides are produced. Among them, aluminum-containing oxides show excellent activities for the cracking of cumene even at low temperature, 523 K, in spite of their amorphous nature.     

LC–MS–MS determination of ibuprofen, 2-hydroxyibuprofen enantiomers,and carboxyibuprofen stereoisomers for application in biotransformation studies employing endophytic fungi

The purpose of this study was the development and validation of an LC–MS–MS method for simultaneous analysis of ibuprofen (IBP), 2-hydroxyibuprofen (2-OH-IBP) enantiomers, and carboxyibuprofen (COOH-IBP) stereoisomers in fungi culture medium, to investigate the ability of some endophytic fungi to biotransform the chiral drug IBP into its metabolites. Resolution of IBP and the stereoisomers of its main metabolites was achieved by use of a Chiralpak AS-H column (150 × 4.6 mm, 5 μm particle size), column temperature 8 °C, and the mobile phase hexane–isopropanol–trifluoroacetic acid (95: 5: 0.1, v/v) at a flow rate of 1.2 mL min⁻¹. Post-column infusion with 10 mmol L⁻¹ ammonium acetate in methanol at a flow rate of 0.3 mL min⁻¹ was performed to enhance MS detection (positive electrospray ionization). Liquid–liquid extraction was used for sample preparation with hexane–ethyl acetate (1:1, v/v) as extraction solvent. Linearity was obtained in the range 0.1–20 μg mL⁻¹ for IBP, 0.05–7.5 μg mL⁻¹ for each 2-OH-IBP enantiomer, and 0.025–5.0 μg mL⁻¹ for each COOH-IBP stereoisomer (r ≥ 0.99). The coefficients of variation and relative errors obtained in precision and accuracy studies (within-day and between-day) were below 15%. The stability studies showed that the samples were stable (p > 0.05) during freeze and thaw cycles, short-term exposure to room temperature, storage at −20 °C, and biotransformation conditions. Among the six fungi studied, only the strains Nigrospora sphaerica (SS67) and Chaetomium globosum (VR10) biotransformed IBP enantioselectively, with greater formation of the metabolite (+)-(S)-2-OH-IBP. Formation of the COOH-IBP stereoisomers, which involves hydroxylation at C3 and further oxidation to form the carboxyl group, was not observed.     

In-line solid-phase extraction–capillary electrophoresis coupled with mass spectrometry for determination of drugs of abuse in human urine

In-line solid-phase extraction–capillary electrophoresis coupled with mass spectrometric detection (SPE–CE–MS) has been used for determination of 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), codeine (COD), hydrocodeine (HCOD), and 6-acetylmorphine (6AM) in urine. The preconcentration system consists of a small capillary filled with Oasis HLB sorbent and inserted into the inlet section of the electrophoresis capillary. The SPE–CE–MS experimental conditions were optimized as follows: the sample (adjusted to pH 6.0) was loaded at 930 mbar for 60 min, elution was performed with methanol at 50 mbar for 35 s, 60 mmol L⁻¹ ammonium acetate at pH 3.8 was used as running buffer, the separation voltage was 30 kV, and the sheath liquid at a flow rate of 5.0 μL min⁻¹ was isopropanol–water 50:50 (v/v) containing 0.5% acetic acid. Analysis of urine samples spiked with the four drugs and diluted 1:1 (v/v) was studied in the linear range 0.08–10 ng mL⁻¹. Detection limits (LODs) (S/N = 3) were between 0.013 and 0.210 ng mL⁻¹. Repeatability (expressed as relative standard deviation) was below 7.2%. The method developed enables simple and effective determination of these drugs of abuse in urine samples at the levels encountered in toxicology and doping.     

Large pore volume mesoporous aluminum oxide synthesized via nano-assembly

A new nano-assembly approach has been proposed for the preparation of macropore volume mesoporous aluminum oxide supports. Secondary nano-assembly and a frame structure mechanism for large pore volume mesoporous supports have been proposed. In a primary nano-assembly supersoluble micelle, aluminum hydroxide nanoparticles were precipitated in situ in surfactants with a volume balance (VB) less than 1, followed by secondary nano-assembly in linear and cylindrical shapes. The secondary nano-assembly of cylindrical aluminum hydroxides was calcined to form nano cylindrical aluminum oxides. For the formation of macropore volume mesoporous supports, we utilized a frame structure mechanism of mesoporous support, in which the exterior surface of the carrier may not be continuous. This macropore volume support has been used for the hydrotreatment of a residual oil catalyst, which possesses the following physical characteristics: pore volume 1.8–2.7 mL·g⁻¹, specific surface area 180–429 m²·g⁻¹, average pore diameter 17–57 nm, average pore diameter more than 10 nm (81%–94%), porosity 87%–93%, and crush strength 7.7–25 N·mm⁻¹.     

Organo-modified mesoporous silica for sorption of carbon dioxide

Abstract  

Organo-modified mesoporous silica SBA-15 has been studied for sorption of carbon dioxide (CO₂). The SBA-15 sample was functionalized with a branched chain polymer, polyethylenimine (PEI), of different molecular weights (1,300 and 2,000 g mol⁻¹). Surface modification was carried out by impregnation of silica by PEI or by grafting with (3-chloropropyl)triethoxysilane, followed by substitution of chlorine atoms by PEI ligands. The prepared modified mesoporous materials were characterized by nitrogen adsorption/desorption at 77 K, high-resolution transmission electron microscopy, small-angle X-ray scattering, and thermal methods. Sorption of CO₂ was studied by gravimetric method at 303 K. The total amount of sorbed CO₂ varied between 0.19–0.67 mmol/g for respective samples. Regeneration of the materials after adsorption was achieved by thermal treatment at 343 K.     

Fast screening immunoassay of sulfonamides in commercial fish samples

An indirect competitive enzyme-linked immunosorbent assay (ELISA) was developed in plate to detect three sulfonamide residues (sulfamerazine (SMR), sulfadimetoxine (SDM), and sulfadiazine (SDZ)) in gilthead sea bream (Sparus aurata) samples. Different extraction methodologies—using methanol/water 1:1 (v/v) + ethylene diamine tetraacetic acid (EDTA) 0.5% (m/v), acetonitrile, phosphate-buffered saline (PBS) 10 mmol L⁻¹ pH 7 and acetate buffer 100 mmol L⁻¹ pH 5—and cleanup steps, based on solid-phase extraction (C₁₈, SCX, Si) or liquid extraction with hexane, were assayed. As optimum, a fast and simple method using acetonitrile was selected to extract the sulfonamide residues from the edible muscle of fish. Due to matrix effects, a standard addition calibration curve in fish extract is necessary for quantification purposes. Sulfonamide-free samples were spiked at different concentration levels (between 30 and 90 ng g⁻¹, 5–15 ng mL⁻¹ in plate) and average recoveries (n = 8), ranging from 71% to 95%, 65% to 79%, and 72% to 95%, were obtained for SMR, SDM, and SDZ, respectively. The assay detection limits for these antibiotics were lower than 100 μg kg⁻¹ (maximum residue level established by the European Union). The accuracy was evaluated by spiking blank fish extracts at different concentrations (10–40 ng mL⁻¹, 5–20 ng mL⁻¹ in plate), and the relative errors ranged between ±20%. Finally, in order to confirm the utility of the developed ELISA as a screening methodology, fish samples from different supermarkets were analyzed, and results were compared with those obtained by a validated high-performance liquid chromatography (HPLC) method. The correlation between the results obtained by both ELISA and HPLC methods is satisfactory.      

Preparation of amino-functionalized mesoporous silica thin films with highly ordered large pore structures

Highly ordered amino-functionalized mesoporous silica thin films have been directly synthesized by co-condensation of tetraethoxysilane (TEOS) and 3-aminopropyltriethoxysilane (APTES) in the presence of triblock copolymer Pluronic P123 surfactant species under acidic conditions by sol-gel dip-coating. The effect of the sol aging on thin films organization is systematically studied, and the optimal sol aging time is obtained. The amino-functionalized mesoporous silica thin films exhibit a long-range ordering of 2D hexagonal (p6mm) mesostructure with a large pore size of 8.3 nm, a large Brunauer–Emmett–Teller (BET) specific surface area of 680 m² g⁻¹ and a large pore volume of 1.06 cm³ g⁻¹ following surfactant extraction as demonstrated by X-ray diffraction (XRD), Transmission electron microscope (TEM), and physical adsorption techniques. Based on BET surface area and weight loss, the surface coverage of amino-groups for the amino-functionalized mesoporous silica thin films is calculated to be 3.2 amino-groups per nm². Moreover, the functionalized thin films display improved properties for immobilization of cytochrome c in comparison with pure-silica mesoporous thin films.     

Direct electrochemistry and biocatalysis of glucose oxidase immobilized on magnetic mesoporous carbon

A magnetic mesoporous carbon material (i.e., mesoporous iron oxide/C, mesoFe/C) is synthesized for protein immobilization, using glucose oxidase (GOx) as model. Transmission electron microscopy images show that mesoFe/C has highly ordered porous structure with uniform pore size, and iron oxide nanoparticles are dispersed along the wall of carbon. After adsorption of GOx, the GOx-mesoFe/C composite is separated with magnet. The immobilized GOx remains its natural structure according to the reflection–absorption infrared spectra. When the GOx-mesoFe/C composite is coated on a Pt electrode surface, the GOx gives a couple of quasireversible voltammetric peaks at −0.5 V (vs. saturated calomel electrode) due to the redox of FAD/FADH₂. The electron-transfer rate constant (k _s) is ca. 0.49 s⁻¹. The modified electrode presents remarkably amperometric response to glucose at 0.6 V. The response time (t _95%) is less than 6 s; the response current is linear to glucose concentration in the range of 0.2–10 mM with a sensitivity of 27 μA mM⁻¹ cm⁻². The detection limit is 0.08 mM (S/N = 3). The apparent Michaelis–Menten constant (K _m^app) of the enzyme reaction is ca. 6.6 mM, indicating that the GOx immobilized with mesoFe/C has high affinity to the substrate.     

Influence of the Solvent Properties on MCM-41 Surface Modification of Aminosilanes

Novel CO₂ adsorbents were prepared by grafting aminosilanes on mesoporous silica MCM-41. The effects of solvent and temperature on the grafting of the amine group were studied. The results of thermal gravimetric analysis of the AEAPDMS-MCM-41s produced in different solvents revealed that the nonpolar solvent toluene and the aprotic polar solvent THF are beneficial to the amine group modification reaction. The CO₂ adsorption capacity of AEAPDMS-MCM-41s produced in toluene had a relatively high value of 2.20 mmol⋅g⁻¹.     

Callus induction and plant regeneration from different explants of Actinidia deliciosa

In this study, an efficient procedure was developed for callus induction and regeneration of kiwifruit (Actinidia deliciosa) using different organs of shoots developed under in vitro conditions. Effects of explants source and media (M₁, 1.0 mg l⁻¹ BA + 2.0 mg l⁻¹ 2,4-D–M₂, 1.0 mg l⁻¹ NAA + 2.0 mg l⁻¹ 2,4-D) on initiation of callus were examined in order to obtain callus for organogenesis. The best callus for plant regeneration was obtained from leaf explants on Murashige and Skoog’s medium (MS) supplemented with M₂. Formation of callus from leaf of kiwifruit (A. deliciosa) was cultured in MS medium containing different concentration of N⁶-benzylaminopurin (BA; 0.0, 1.0, 2.0, 4.0, 6.0, 8.0 mg l⁻¹) for callus proliferation and plant regeneration. Although the first shoot formation was appeared in medium containing 6.0 and 8.0 mg l⁻¹ BA, the best shoots formation was obtained in medium with 4.0 mg l⁻¹ BA.     

Wood cellulose nanofibrils prepared by TEMPO electro-mediated oxidation

A softwood bleached kraft pulp (SBKP) was subjected to electro-mediated oxidation in water with TEMPO or 4-acetamido-TEMPO without any chlorine-containing oxidant. Solid recovery ratios of water-insoluble fractions of the oxidized SBKPs were more than 80%, and C6-carboxylate contents increased up to approximately 1 mmol g⁻¹ after oxidation for 48 h. Significant amounts of C6-aldehyde groups (0.17–0.38 mmol g⁻¹) were also formed in the oxidized SBKPs. The degree of polymerization decreased from 2,200 to 520 and 1,400 by the oxidation for 48 h with TEMPO at pH 10 and 4-acetamido-TEMPO at pH 6.8, respectively. The original cellulose I crystal structure and crystallinity of SBKP were maintained after the oxidation, indicating that all C6-oxidized groups were selectively formed on crystalline cellulose microfibril surfaces. The oxidized SBKPs with carboxylate contents of more than 0.9 mmol g⁻¹ were convertible to individual cellulose nanofibrils in yields of more than 80% by disintegration in water.     

1,3,5,7-Tetramethyl-8-(<Emphasis Type="Italic">N</Emphasis>-hydroxysuccinimidyl butyric ester)difluoroboradiaza-<Emphasis Type="Italic">s</Emphasis>-indacene as a new fluorescent labeling reagent for HPLC determination of amino acid neurotransmitters in the cerebral cortex of mice

1,3,5,7-Tetramethyl-8-(N-hydroxysuccinimidyl butyric ester)difluoroboradiaza-s-indacene (TMBB-Su), a new BODIPY-based fluorescent probe, was designed and synthesized for the labeling of amino compounds. It was used as a pre-column derivatizing reagent for determination of amino acid neurotransmitters by high-performance liquid chromatography (HPLC). The fluorescence quantum yield in acetonitrile increased from 0.84 to 0.95 when it reacted with amino acid neurotransmitters. Derivatization of TMBB-Su with seven amino acid neurotransmitters was completed within 30 min at 25 °C in 24.0 mmol L⁻¹ pH 7.8 boric acid buffer. The separation was performed on a C₁₈ column with methanol–water–buffer 55:35:10 (v/v) as mobile phase (buffer: 0.10 mol L⁻¹ H₃Cit–0.10 mol L⁻¹ NaOH). Interference from the other concomitant amino acids was eliminated successfully by means of pH gradient elution. With fluorescence detection at 494 and 504 nm for excitation and emission, respectively, the limits of detection (signal-to-noise ratio = 3) were from 2.1 to 12.0 nmol L⁻¹. The proposed method has been used to determine amino acid neurotransmitters in the cerebral cortex of mice with cerebral ischemia at the convalescence stage with satisfactory recoveries varying from 94.9 to 105.2%.     

Adsorption heats of phenol on activated carbon using adapted method of immersion calorimetry

Simple adaptation of the technique of immersion calorimetry enables determining both integral and differential adsorption heats as well as the course of the adsorption isotherm of phenol on activated carbon. The innovative aspect of the applied procedure consists in bringing the phenol aqueous solution to contact with the suspension of carbon with water. Thus, the “interfering” heat effect of carbon interaction with water is eliminated, and only the net adsorption heat of phenol is monitored. The value of −52.5 kJ mol⁻¹ was ascertained as the molar differential adsorption heat at the low surface coverage (cca 0.2 mmol g⁻¹) of the sample of microporous carbon. As the adsorption process continues, for adsorption uptakes exceeding the value of about 1 mmol g⁻¹, molar differential adsorption heats appear to be established at a level of about −20 + 5 kJ mol⁻¹.     

Synthesis and characterization of mesoporous Mn–Ni oxides for supercapacitors

Mesoporous Mn–Ni oxides with the chemical compositions of Mn_1-x Ni _x O _δ (x = 0, 0.2, and 0.4) were prepared by a solid-state reaction route, using manganese sulfate, nickel chloride, and potassium hydroxide as starting materials. The obtained Mn–Ni oxides, mainly consisting of the phases of α- and γ-MnO₂, presented irregular mesoporous agglomerates built from ultra-fine particles. Specific surface area of Mn_1–x Ni _x O _δ was 42.8, 59.6, and 84.5 m² g⁻¹ for x = 0, 0.2, and 0.4, respectively. Electrochemical properties were investigated by cyclic voltammetry and galvanostatic charge/discharge in 6 mol L⁻¹ KOH electrolyte. Specific capacitances of Mn_1-x Ni _x O _δ were 343, 528, and 411 F g⁻¹ at a scan rate of 2 mV s⁻¹ for x = 0, 0.2, and 0.4, respectively, and decreased to 157, 183, and 130 F g⁻¹ with increasing scan rate to 100 mV s⁻¹, respectively. After 500 cycles at a current density of 1.24 A g⁻¹, the symmetrical Mn_1–x Ni _x O _δ capacitors delivered specific capacitances of 160, 250, and 132 F g⁻¹ for x = 0, 0.2, and 0.4, respectively, retaining about 82%, 89%, and 75% of their respective initial capacitances. The Mn_0.8Ni_0.2O _δ material showed better supercapacitive performance, which was promising for supercapacitor applications.     

Iodine determination in food by inductively coupled plasma mass spectrometry after digestion by microwave-induced combustion

Iodine determination in food samples was performed by inductively coupled plasma mass spectrometry (ICP-MS) after digestion by microwave-induced combustion (MIC). Sample masses up to 500 mg of bovine liver, corn starch, milk powder, or wheat flour were completely combusted using the MIC system. Ammonium nitrate (6 mol l⁻¹ solution, 50 μl) was used as an aid for ignition and vessels were charged with 15 bar of O₂. The use of H₂O, 0.9 mmol l⁻¹ H₂O₂, 10 to 50 mmol l⁻¹ (NH₄)₂CO₃ and 56 mmol l⁻¹ tetramethylammonium hydroxide was investigated as absorbing solutions, as well as the suitability of performing a reflux step after the combustion process. Digestion of food samples by pressurized microwave-assisted acid digestion, microwave-assisted extraction and conventional extraction of iodine in alkaline solution were also evaluated. Iodine recoveries higher than 99% were obtained using MIC and 50 mmol l⁻¹ (NH₄)₂CO₃ or 56 mmol l⁻¹ tetramethylammonium hydroxide as absorbing solution and with 5 min for the reflux step. Accuracy was evaluated using certified reference materials (bovine muscle, corn bran, and milk powder) and agreement better than 97% was obtained. The limit of quantification by MIC and further ICP-MS determination was 0.002 μg g⁻¹. Blanks were always low and no memory effects were observed. Digestion by MIC allowed the processing of up to eight samples by each run in 25 min with high efficiency of digestion (residual carbon content lower than 1%) providing a suitable medium for further iodine determination by ICP-MS.     

Intermediate and ion-pair formation in the outer-sphere reactions between azido-pentacyanocobaltate(III) and iron(II) polypyridyl complexes in aqueous medium

The kinetics of the reactions between azido-pentacyanocobaltate(III), Co(CN)₅N₃ ³⁻, and iron(II) polypyridyl complexes, Fe(LL)₃ ²⁺ (LL = bipy, phen), have been studied in both neutral and acidic aqueous solutions at I = 0.1 mol dm⁻³ NaCl. The reactions were carried out under pseudo-first-order conditions in which the concentration of Fe(LL)₃ ²⁺ was kept constant, and the second-order rate constants obtained for the reactions at 35 °C were within the range of 0.156–0.219 dm³ mol⁻¹ s⁻¹ for LL = bipy and 0.090–0.118 dm³ mol⁻¹ s⁻¹ for LL = phen. Activation parameters were measured for these systems. The dependence of reaction rates on acid was studied in the range [H⁺] = 0.001–0.008 mol dm⁻³. The reaction in acid medium shows interesting kinetics. Two reactive species were identified in acid medium, namely, the protonated cobalt complex and the azido-bridged binuclear complex. The electron-transfer process is proposed to go by mixed outer- and inner-sphere mechanisms in acid medium, in which electron transfer through the bridged inner-sphere complex (k ₅) is slower than through the outer-sphere path (k ₄). Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Design of silica microparticles with oligopeptide brushes and their interaction with proteins

Synthesis of small oligopeptide brushes (oligo(S-benzyl-l-cysteine)) onto polyelectrolyte functionalized silica microparticles was developed. Poly(vinyl amine) (PVAm) adsorbed from salt-free and KCl 10⁻¹ mol L⁻¹ aqueous solution onto silica microparticles was chemically and naturally cross-linked by epichlorohydrin and CO₂, respectively. After the adsorption of PVAm onto microporous silica particles and stabilization by cross-linking, five repeated coupling reactions of Boc-S-benzyl-l-cysteine were performed. To test the protein interactions with the newly designed surface, human serum albumin (HSA) has been selected as a model protein. X-ray photoelectron spectroscopy, total organic carbon, potentiometric and polyelectrolyte titrations, and electrokinetic analysis were employed to obtain information about the polyelectrolyte adsorption and the amount of the amino acid S-benzyl-l-cysteine that was covalently bound to the solid surface and for determination of the protein amount adsorbed onto functionalized surface. The amount of HSA adsorbed onto modified silica microparticles decreased in order: silica/PVAm-cross-linked (silica/PVAm-C) (8.00 mg g⁻¹) > silica/PVAm-C/S-benzyl-l-cysteine (6.34 mg g⁻¹) > silica (4.86 mg g⁻¹) > silica/PVAm-C/(S-benzyl-l-cysteine)₅ (1.86 mg g⁻¹).     

Chiral separation of ofloxacin enantiomers by ligand exchange chromatography

Abstract  

The enantioseparation conditions of ligand exchange chromatography were examined using ofloxacin enantiomers. A C₁₈ column was used with the mobile phase consisting of a methanol–water solution (containing different concentrations of l-isoleucine and copper sulfate) at flow rate of 0.5 cm³ min⁻¹. The effect of different kinds and concentrations of ligands, bivalent ligand ions, and organic modifier, and temperature on enantioseparation were evaluated; the results showed that enantioselectivity was strongly affected by the ligand concentration of the mobile phase. Under the optimum conditions (methanol/water 20:80 v/v, containing 2.5 mmol dm⁻³ l-isoleucine and 0.6 mmol dm⁻³ Cu²⁺, room temperature), baseline separation of the two enantiomers was obtained with resolution of 1.32 in less than 30 min. The separation method was used to analyze the ofloxacin enantiomers in different commercial medicines.