Elucidating the Stereochemistry of Enzymatic Benzylsuccinate Synthesis with Chirally Labeled Toluene

Benzylsuccinate synthase is a glycyl radical enzyme that initiates anaerobic toluene metabolism by adding fumarate to the methyl group of toluene to yield (R)‐benzylsuccinate. To investigate whether the reaction occurs with retention or inversion of configuration at the methyl group of toluene, we synthesized both enantiomers of chiral toluene with all three H isotopes in their methyl groups. The chiral toluenes were converted into benzylsuccinates preferentially containing ²H and ³H at their benzylic C atoms, owing to a kinetic isotope effect favoring hydrogen abstraction from the methyl groups. The configuration of the products was analyzed by enzymatic CoA‐thioester synthesis and stereospecific oxidation using enzymes involved in benzylsuccinate degradation. Assessment of the configurations of the benzylsuccinate isomers based on loss or retention of tritium showed that inversion of configuration at the methyl group occurs when the chiral toluenes react with fumarate.     

The generalization of the generalized Al-Oboudi differential operator

In this paper, firstly we define the generalization of the generalized Al-Oboudi differential operator. Then we also define new classes of analytic and p-valently starlike and convex functions with complex order by means of this new general differential operator. Our main purpose is to determine coefficient bounds for functions in certain subclasses of this classes, which are introduced here by means of a family of nonhomogeneous Cauchy-Euler differential equations. Relevant connections of some of the results obtained with those in earlier works are also provided.     

Use of ionic liquid based chitosan as sorbent for preconcentration of fluoroquinolones in milk,egg, fish,bovine, and chicken meat samples by solid phase extraction prior to HPLC determination

The possibility of using ionic liquid based chitosan sorbent for the separation and preconcentration of fluoroquinolone antibiotics (marbofloxacin, enoxacin, ofloxacin, ciprofloxacin, and enrofloxacin) has been studied. For this reason, different ionic liquids were prepared and coated on the chitosan sorbent. The conditions of the preconcentration of fluoroquinolones on a microcolumn have been optimized and the extraction efficiencies of the prepared sorbents have been compared. The compounds were eluted with 5 mL of 20% NH₃ (v/v, MeOH) solution and determined by HPLC with diode array and fluorescence detector. The limits of detection were found as 4.23 µ g L^?1 for marbofloxacin, and 1.09 µg L^?1 for enoxacin; 3.23 × 10^?3 µg L^?1 for ofloxacin; 8.39 × 10^?3 µg L^?1 for ciprofloxacin; and 19.50 × 10^?3 µg L^?1 for enrofloxacin. The developed method was applied for the analysis of fluoroquinolone in milk, egg, fish, bovine, and chicken samples and the recoveries were obtained in the range 70–100%.     

Conversion of a cyclotriphosphazene to a cyclohexaphosphazene by ring expansion

Deprotonation of a cyclotriphosphazene with a tert-butylamino group in the side chain results in ring expansion to a very stable, planar cyclohexaphosphazene derivative that still contains eight P-Cl bonds suitable for forming macromolecular structures.     

Preparation of bow tie–type methacrylated poly(caprolactone‐co‐lactic acid) scaffolds: effect of collagen modification on cell growth

A branched methacrylated poly(caprolactone‐co‐lactic acid) and methacrylated poly(tetramethylene ether glycol) (PTMG‐IEM) resins were synthesized. ¹H‐NMR spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR) spectroscopy, and gel permeation chromatography confirmed the chemical structures of copolymers. The photoinitiated polymerization of formulation composed of various amounts of methacrylated poly(caprolactone‐co‐lactic acid), PTMG‐IEM, poly(ethylene glycol) diacrylate, water, and photoinitiator were performed. The curing reactions were followed by photo‐DSC (Differential scanning calorimetry). Gel fraction was calculated from the insoluble part and found as ≥93%. Swelling and contact angles were measured, and all increased with the increasing amount of PTMG‐IEM in network formulations. In vitro degradation studies were performed at 37 °C in phosphate‐buffered saline (pH 7.4). Collagen‐modified polymers were also prepared and introduced as a bioactive moiety to modify the polymer to enhance cell affinity. To compare the cell adhesion affinity to the polymer with and without collagen, cell growth experiments were performed. The results showed that collagen improves the cell adhesion onto the polymer surface. With the increasing amount of collagen, cell viability increases 86% (ECV304, p < 0.05) and 83% (3 T3, p < 0.05). Copyright © 2011 John Wiley & Sons, Ltd.     

Surface and chemical characteristics of platinum modified activated carbon electrodes and their electrochemical performance

Platinum (Pt) loaded activated carbons (ACs) were synthesized by the thermal decomposition of platinum (II) acetylacetonate (Pt(acac)₂) over chemically activated glucose-based biochar. The effect of Pt loading on surface area, pore characteristics, surface chemistry, chemical structure, and surface morphology were determined by various techniques. XPS studies proved the presence of metallic Pt⁰ on the AC surface. The graphitization degree of Pt loaded ACs were increased with the loaded Pt⁰ amount. The electrochemical performance of the Pt-loaded ACs (Pt@AC) was determined not only by the conventional three-electrode system but also by packaged supercapacitors in CR2032 casings. The capacitive performance of Pt@AC electrodes was investigated via cyclic voltammetry (CV), galvanostatic charge-discharge curves (GCD), and impedance spectroscopy (EIS). It was found that the Pt loading increased the specific capacitance from 51 F/g to 100 F/g. The ESR drop of the packaged cell decreased with the Pt loading due to the fast flow of charge through the conductive pathways. The results showed that the surface chemistry is more dominant than the surface area for determining the capacitive performance of Pt loaded AC-based packaged supercapacitors.     

Epimeric Isopavine N-Oxides from Roemeria refracta

Roemeria refracta DC. (Papaveraceae) of Turkish origin yielded two novel epimeric N-oxides, (?)-(5R, 11S,14R)-reframidine N-oxide ( = (?)-(5R, 11S,14R)-11,12-dihydro-14-methyl-11,5-(iminomethano)-5H -cyclohepta[1, 2-f: 4, 5-f′]bis[1,3]benzodioxole 14-oxide; 1 ) and (?)-(5R, 11S, 14S)-reframidine N-oxide ( = (?)-(5R, 11S, 14S)-11, 12-dihydro-14-methyl-11, 5-(iminomethano)-5H-cyclohepta[1, 2-f:4, 5-f′]bis[1, 3]benzodioxole 14-oxide; 2 ). The isolated (?)-roelactamine ( = (?)-11, 12-dihydro-14-methyl-11, 5-(iminomethano)-5H-cyclohepta[1, 2-f:4, 5-f′]bis[1, 3]benzodioxol-15-one, 4 ) is the first natural isopavinoid incorporating a lactam group. The epimeric (?)-15-(2-oxopropyl)reframidines ( = (?)-1-[11, 12-dihydro-14-methyl-11, 5-(iminomethano)-5H-cyclohepta[1, 2-f:4, 5-f′]bis[1, 3]benzodioxol-15-y1]propan-2-ones; 5/6 ) and the epimeric (?)-ethyl (reframidin-15-yl)acetates ( = (?)-ethyl [11, 12-dihydro-14-methyl-11, 5-(iminomethano)-5H-cyclohepta[1, 2-f:4, 5-f′]bis[1, 3]benzodioxol-15-y1]acetates; 7/8 ) are probably artifacts. (±)-Coclaurine ( 9 ), (±)-N-methylcoclaurine ( 10 ), (?)-roemeridine ( 11 ), and N-feruloyltyramine ( 12 ) are also isolated from R. refracta together with the previously reported bases. Specific ¹³C-NMR assignments are reported for the first time for the isopavines.     

Kinetics and modeling of (R,S)‐1‐phenylethanol acylation over lipase

The kinetics of the acylation of (R,S)‐1‐phenylethanol was investigated using lipase as a catalyst. The main parameters were temperature, reaction atmosphere, different acyl donors, and different amounts of acyl donor as well as the presence of some additives in the reaction mixture. The initial reaction rate increased with increasing temperature and with a decreasing amount of an acyl donor. The activated esters, such as isopropenyl‐ and vinyl acetate, exhibited very high acylation rates for R‐1‐phenylethanol, whereas low rates were obtained with ethyl acetate and 2‐methoxyethyl acetate. The addition of water and acetophenone decreased the acylation rate. A kinetic model was developed based on a sequential step mechanism, in which enzyme was reacting in the first step with an acyl donor followed by the reaction of a modified enzyme complex with the reactant, R‐1‐phenylethanol. Comparison with experimental data obtained at different temperatures allowed simplification of this model, leading to a kinetic equation with just one apparent parameter. The influence of the amount of acyl donor, ethyl acetate, could be quantitatively described by taking into account the competitive inhibition of the ethanol produced. The rate constants and apparent activation energy for experiments performed under different temperatures and the amounts of acylation agent were determined. The apparent activation energy was 24.5 kJ/mol. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 629–639, 2010     

Formation of spiro and ansa derivatives in the reaction of 2,2,3,3,4,4-hexafluoropentane-1,5-diol with cyclotriphosphazene: Comparison with 2,2,3,3-tetrafluorobutane-1,4-diol

Reaction of cyclophosphazene, N₃P₃Cl₆ (1), with the sodium derivative of the fluorinated diol, 2,2,3,3,4,4-hexafluoropentane-1,5-diol (2), in THF solution at room temperature afforded five isolated products, whose structures have been characterised by X-ray crystallography and ¹H, ¹⁹F and ³¹P NMR spectroscopy: the mono-spiro compound, N₃P₃Cl₄(OCH₂CF₂CF₂CF₂CH₂O) (3), its ansa isomer (4), a di-spiro derivative N₃P₃Cl₂(OCH₂CF₂CF₂CF₂CH₂O)₂ (5), its spiro-ansa (6) isomer and the tri-spiro compound N₃P₃(OCH₂CF₂CF₂CF₂CH₂O)₃ (7). Quantitative ³¹P NMR measurements of the soluble portion of the reaction mixture show that in the reaction of (1) with the sodium derivative of the fluorinated pentanediol (2) there is a small preference for spiro compounds compared to ansa compounds (ratio ca. 1.3:1), similar to the analogous reaction of (1) with the sodium derivative of the fluorinated butanediol where there is a slightly greater proportion of spiro compared to ansa compounds (ratio ca. 1.5:1). The relative proportions of spiro and ansa compounds is likely to depend on the fine balance in stabilities of the different medium-sized rings in the fluorinated pentanediol (spiro, 8- and ansa, 10-membered rings) compared to the fluorinated butanediol (spiro, 7- and ansa, nine-membered rings) derivatives of cyclophosphazene.     

Comparison of high-performance liquid chromatography of cyclotriphosphazene derivatives with one or two equivalent stereogenic centres

High-performance liquid chromatographic (HPLC) methods have been developed for investigating the stereogenic properties of two analogous series of dibenzylamino derivatives of cyclotriphosphazene containing either one or two equivalent stereogenic centres. Separation of the enantiomers of all the racemic compounds has been investigated by chiral HPLC using Whelk-01 and Chiralcel OD columns. In all cases, conditions for separation of enantiomers have been found using a Whelk-01 column with different ratios of tetrahydrofuran in n-hexane as the mobile phase. It is found that both the separation factor (alpha) and resolution factor (R(S)) of molecules with two equivalent stereogenic centres are greater than those for analogues with only one centre.