Servet Tural

Carboligation Reactions Mediated by Benzoylformate Decarboxylase Immobilized on a Magnetic Solid Support

In this study, magnetic nanoparticles (Fe3 O4 , magnetite) with immobilized metal affinity ligands (MSS) were prepared and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FTIR), and vibrating-sample magnetometer (VSM) methods for purification and immobilization of the histidine-tagged recombinant benzoylformate decarboxylase (BFD). The MSS support was shown to be eligible for selective binding of HIS-tagged BFD by SDS-page analysis. Loading capacity of the MSS support was determined as 43.6 ± 1.1 mg/g. The regeneration ability for protein binding was also studied. An immobilized BFD was tested to catalyze benzoin condensation and representative cross acyloin reaction. Conversion and enantiomeric excess values were comparable with that of free enzyme catalyzed reactions.

SOLVENT EXTRACTION OF BORON WITH l,2-DIHYDROXY-4-OXADODECANE (DHD) IN n-AMYL ALCOHOL

ABSTRACT In the work presented here, l,2-dihidroxy-4-oxadodecane (DHD) was synthesized and used for the solvent extraction of boron. DHD was prepared from glycidol and octanol by thermal epoxide ring opening reaction without using acid or base catalyst. The structure of this new extracting reagent was identified according to its spectroscopic data i.e. 13C NMR, 1H NMR and elemental analysis results. The fixed standard solution of boron (as borax) of 10−4 M was extracted with different volume ratios of DHD and n-amyl alcohol (AA) at different equilibrium pH values. The best extraction result was obtained at high pH values with a mixture of equal volumes of DHD and n-amyl alcohol. The different equilibrium pH values were plotted against the extraction yields (%R) and the pH0·5 value was determined by using this graph. The extraction of boron from aqueous solutions with equal volumes of DHD and various solvents were studied and it was found that petroluem ether, n-amyl alcohol and diisopropyl ether are convi...

Kinetic approach for the purification of nucleotides with magnetic separation.

The isolation of β-nicotinamide adenine dinucleotide is of great importance since it is widely used in different scientific and technologic fields such as biofuel cells, sensor technology, and hydrogen production. In order to isolate β-nicotinamide adenine dinucleotide, first 3-aminophenyboronic acid functionalized magnetic nanoparticles were prepared to serve as a magnetic solid support and subsequently they were used for reversible adsorption/desorption of β-nicotinamide adenine dinucleotide in a batch fashion. The loading capacity of the 3-aminophenyboronic acid functionalized nanoparticles for β-nicotinamide adenine dinucleotide adsorption was 13.0 μmol/g. Adsorption kinetic and isotherm studies showed that the adsorption process followed a pseudo-second-order kinetic model and the experimental data can be represented using Langmuir isotherm model. The 3-aminophenyboronic acid functionalized magnetic nanoparticles were proposed as an alternative support for the β-nicotinamide adenine dinucleotide purification. The results elucidated the significance of magnetic separation as a fast, relatively simple, and low-cost technique. Furthermore, the magnetic supports can be reused at least five times for purification processes.

Effect of 1,3-Diol Structure on the Distribution of Boron Between CHCl3 and Aqueous Phase

The various new aliphatic 1,3-diols, containing primary, secondary, tertiary, and mixed of these groups, were synthesized and used for the solvent extraction of boron. Diols (8a, 8b, 9, 10a, 10b, 11, 12a, 12b, 13) were prepared from (β-hydroxy carbonyl compounds 1–7. The fixed standard solution of boric acid of 1.00×10−2 M was extracted with 0.1 M and 0.5 M diols at equilibrium pH of 2 and at constant ionic strength (I=0.5). The best extracting reagent was found to be 11, which is a primary–tertiary class of -OH groups and methyl groups as a substituent on the second carbon of 1,3-diol.

Enantioseparation of Mandelic Acid Enantiomers With Magnetic Nano-Sorbent Modified by a Chiral Selector

In this study, R(+)-α-methylbenzylamine-modified magnetic chiral sorbent was synthesized and assessed as a new enantioselective solid phase sorbent for separation of mandelic acid enantiomers from aqueous solutions. The chemical structures and magnetic properties of the new sorbent were characterized by vibrating sample magnetometry, transmission electron microscopy, Fourier transform infrared spectroscopy, and dynamic light scattering. The effects of different variables such as the initial concentration of racemic mandelic acid, dosage of sorbent, and contact time upon sorption characteristics of mandelic acid enantiomers on magnetic chiral sorbent were investigated. The sorption of mandelic acid enantiomers followed a pseudo-second-order reaction and equilibrium experiments were well fitted to a Langmuir isotherm model. The maximum adsorption capacity of racemic mandelic acid on to the magnetic chiral sorbent was found to be 405 mg g(-1). The magnetic chiral sorbent has a greater affinity for (S)-(+)-mandelic acid compared to (R)-(-)-mandelic acid. The optimum resolution was achieved with 10 mL 30 mM of racemic mandelic acid and 110 mg of magnetic chiral sorbent. The best percent enantiomeric excess values (up to 64%) were obtained by use of a chiralpak AD-H column.

The Solvent Extraction of Boron with Synthesized Aliphatic 1,3‐Diols: Stripping and Extraction Behavior of Boron by 2,2,5‐Trimethyl‐1,3‐hexanediol

Abstract A variety of aliphatic 1,3‐diols (4a–c, 5a–c, 6a–c) was synthesized from β‐hydroxy carbonyl compounds (1–3) for potential use in the solvent extraction of boron. Primary‐secondary and primary‐tertiary alcohol structures of 1,3‐diols substituted with isopropyl, isobutyl, and isopentyl groups have been demonstrated to be very efficient for the solvent extraction of boric acid from aqueous solutions. The extraction ability of 2,2,5‐trimethyl‐1,3‐hexanediol (5b) was investigated as a function of 5b concentration, solution pH, solvent properties, and stripping conditions. Extraction efficiency increased with increasing concentration of 5b, and the best extraction of boron (96.8%) was found to be at an equilibrium pH of 2 with 0.5 M of 5b. Chloroform, toluene, chlorobenzene, 2‐octanol, and n‐amyl alcohol were found to be suitable solvents for the solvent extraction of boron. The boron complex can be recovered from the organic phase by treatment with an aqueous solution of sodium hydroxide. The highest ratio (96.7%) of boron was recovered by 0.1 M of sodium hydroxide solution.

Heterofunctional Magnetic Metal-Chelate-Epoxy Supports for the Purification and Covalent Immobilization of Benzoylformate Decarboxylase From Pseudomonas Putida and Its Carboligation Reactivity

In this study, the combined use of the selectivity of metal chelate affinity chromatography with the capacity of epoxy supports to immobilize poly-His-tagged recombinant benzoylformate decarboxylase from Pseudomonas putida (BFD, E.C. 4.1.1.7) via covalent attachment is shown. This was achieved by designing tailor-made magnetic chelate-epoxy supports. In order to selectively adsorb and then covalently immobilize the poly-His-tagged BFD, the epoxy groups (300 µmol epoxy groups/g support) and a very small density of Co(2+)-chelate groups (38 µmol Co(2+)/g support) was introduced onto magnetic supports. That is, it was possible to accomplish, in a simple manner, the purification and covalent immobilization of a histidine-tagged recombinant BFD. The magnetically responsive biocatalyst was tested to catalyze the carboligation reactions. The benzoin condensation reactions were performed with this simple and convenient heterogeneous biocatalyst and were comparable to that of a free-enzyme-catalyzed reaction. The enantiomeric excess (ee) of (R)-benzoin was obtained at 99 ± 2% for the free enzyme and 96 ± 3% for the immobilized enzyme. To test the stability of the covalently immobilized enzyme, the immobilized enzyme was reused in five reaction cycles for the formation of chiral 2-hydroxypropiophenone (2-HPP) from benzaldehyde and acetaldehyde, and it retained 96% of its original activity after five reaction cycles.

Removal of phenolic pollutants from aqueous solutions by a simple magnetic separation

AbstractThe removal efficiencies of phenol, 2-chlorophenol (2-CPh), and 4-chlorophenol (4-CPh) from aqueous solution with magnetic chitosan nanoparticles were investigated in this work. Chitosan-coated magnetite nanoparticles were successfully synthesized, characterizated, and applied as an effective magnetic biosorbent for the removal of phenol, 2-CPh, and 4-CPh from aqueous solutions. The characterization of synthesized magnetic chitosan nanoparticles was performed by Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, dynamic light scattering, vibrating sample magnetometry analyses, and thermogravimetric analysis. Adsorption characteristics of phenolic compounds from aqueous solution on to magnetic chitosan have been studied and results indicated that the adsorption capacities were affected by initial pH values, initial concentration of adsorbates, dosage of adsorbent, and contact time. The adsorption of adsorbates followed with the pseudo-second-ord...

Synthesis of novel magnetic nano-sorbent functionalized with N-methyl-D-glucamine by click chemistry and removal of boron with magnetic separation method

Click chemistry refers to a group of reactions that are fast, simple to use, easy to purify, versatile, regiospecific, and give high product yields. Therefore, a novel, efficient magnetic nano-sorbent based on N-methyl-D-glucamine attached to magnetic nanoparticles was prepared using click coupling method. Its boron sorption capacity was compared with N-methyl-D-glucamine direct attached nano-sorbent. The characterization of the magnetic sorbents was investigated by several techniques such as X-ray diffraction, scanning electron microscope, transmission electron microscope, dynamic light scattering, thermogravimetric analysis, Fourier transform infrared spectrophotometer, and vibrating sample magnetometer. The boron sorption capacity of sorbents was compared by studying various essential factors influencing the sorption, like sorbate concentration, sorbents dosage, pH of the solution, and contact time. Langmuir and Freundlich and Dubinin-Radushkevich adsorption isotherms models were applied. Percent removal and sorption capacities efficiencies of sorbents obtained with direct and click coupling are found to be 49.5%, 98.7% and 6.68 mg/g, 13.44 mg/g respectively. Both sorbents have been found to be compatible with Langmuir isotherm, and the boron sorption kinetics conforms to the pseudo second order kinetics. The reusability study of sorbents was carried out five times for boron sorption and desorption.