Eco‐friendly ionic liquid assisted capillary electrophoresis and α‐acid glycoprotein‐assisted liquid chromatography for simultaneous determination of anticancer drugs in human fluids

In the current work, two eco‐friendly analytical methods based on capillary electrophoresis (CE) and reversed phase liquid chromatography (RPLC) were developed for simultaneous determination of the most commonly used anticancer drugs for Hodgkin's disease: methotrexate (MTX), vinblastine, chlorambucil and dacarbazine. A background electrolyte (BGE) of 12.5 mmol/L phosphate buffer at pH 7.4 and 0.1 µmol/L 1‐butyl‐3‐methyl imidazolium bromide (BMImBr) ionic liquid (IL) was used for CE measurements at 250 nm detection wavelength, 20 kV applied voltage and 25 °C. The rinsing protocol was significantly improved to reduce the adsorption of IL on the interior surface of capillary. Moreover, RPLC method was developed on α‐1‐acid glycoprotein (AGP) column. Mobile phase was 10 mmol/L phosphate buffer at pH 6.0 (100% v/v) and flow rate at 0.1 mL/min. As AGP is a chiral column, it was successfully separated l ‐MTX from its enantiomer impurity d ‐MTX. Good linearity of quantitative analysis was achieved with coefficients of determinations (r²) >0.995. The stability of drugs measurements was investigated with adequate recoveries up to 24 h storage time under ambient temperature. The limits of detection were <50 and 90 ng/mL by CE and RPLC, respectively. The using of short‐chain IL as an additive in BGE achieved 600‐fold sensitivity enhancement compared with conventional Capillary Zone Electrophoresis (CZE). Therefore, for the first time, the proposed methods were successfully applied to determine simultaneously the analytes in human plasma and urine samples at clinically relevant concentrations with fast and simple pretreatments. Developed IL‐assisted CE and RPLC methods were also applied to measure MTX levels in patients’ samples over time. Copyright © 2014 John Wiley & Sons, Ltd.     

4-Oxatricyclo[5.2.1.0(2,6)]decan-10-one and 4-oxatricyclo[5.2.1.0(2,6)]dec-8-en-10-one. Experimental and DFT investigations of the pi-selectivities.

Ab initio MO and experimental pi-selectivities of hydride additions to 4-oxatricyclo[5.2.1.0(2,6)]decan-10-one and 4-oxatricyclo[5.2.1.0(2,6)]dec-8-en-10-one are described. The interactions of sigma(C1-C2) and sigma(C6-C7) with pi(C=O), on one hand, and those of sigma(C1-C9) and sigma(C7-C8) with pi(C=O), on the other hand, support anti-selectivities for both. This is in full accordance with the experiments. The arguments that are based on electrostatic interactions and electron donation from the ring oxygen do not apply.     

Oxidation of simple phenols by phenyl iodoso acetate

Kinetic studies on the oxidation of phenol and 4-nitro and 4-methyl phenols by phenyl iodoso acetate are reported here. The reaction rate depends on the dielectric constant of the medium. A probable mechanism for the oxidation is also suggested. The free energies of activation for the oxidation of the three substrates studied are in accordance with the mechanism proposed.     

Photopolymers: Synthesis and Characterization of Poly(3‐methacryloyloxystyryl‐2‐naphthyl ketone)

3‐Methacryloyloxystyryl‐2‐naphthyl ketone containing a photosensitive α,β‐unsaturated ketone moiety was synthesized and polymerized in methyl ethyl ketone using benzoyl peroxide as the initiator. The thermally stable polymer was characterized by means of UV, IR and NMR spectroscopy. The molecular weight data as obtained from gel permeation chromatography suggests a high tendency for chain termination by disproportionation. The photosensitivity of the polymer in the presence and absence of photosensitizers and the effect of solvent on the rate of photocrosslinking (see Figure) was also investigated.     

Scope of AuCl3 in the activation of per-O-acetylglycals

Gold(III)chloride in catalytic amounts activates 3,4,6-tri-O-acetyl-d-glucal, 3,4,6-tri-O-acetyl-d-galactal, and 3,4-di-O-acetyl-l-rhamnal efficiently. The activated species can be employed in the Ferrier reaction with different nucleophiles at ambient conditions. Attempts have been made to make β-anomer of the Ferrier product from anomeric-O-propargylated Ferrier product.     

A Note on Dave's Inventory Model for Deteriorating Items

In this paper an attempt has been made to generalise Dave's results on an inventory model for deteriorating items. He has derived the results for optimal order level and lot size, considering a deterministic constant demand throughout the scheduling period. Here, a variable known demand is taken to show that the optimality conditions for the optimal initial stock do not depend on the nature of the demand. A numerical example is used to illustrate the analysis.     

Synthesis of 1‐Arylnaphthalenes by Gold‐Catalyzed One‐Pot Sequential Epoxide to Carbonyl Rearrangement and Cyclization with Arylalkynes

Intermolecular and intramolecular reactions of a one‐pot gold‐catalyzed epoxide rearrangement followed by an electrophilic addition to arylalkynes to synthesize 1‐arylnaphthalenes have been reported. The intramolecular reaction has been applied to synthesize 1‐arylnaphthalenes fused with saturated furan, pyran, pyrrole, and cyclopentane ring systems.     

Use of short chain alkyl imidazolium ionic liquids for on‐line stacking and sweeping of methotrexate,flinic acid and folic acid: Their application to biological fluids

Methotrexate (MTX) is widely used for the treatment of many types of cancer. Folinic acid (FNA) and folic acid (FA) were usually simultaneously supplemented with MTX to reduce the side effects of a folate deficiency. This study, for the first time, included on‐line sample preconcentration by stacking and sweeping techniques under reduced or enhanced electric conductivity in the sample region using short chain alkyl imidazolium ionic liquids (ILs) as micelle forming agents for analyte focusing. Both analyte focusing by micelle collapse (AFMC) and sweeping‐MEKC had been investigated for the comparison of their effectiveness to examine simultaneously MTX, FNA and FA in plasma and urine under physiological conditions. In sweeping‐MEKC, the sample solution without micelles was hydrodynamically injected as a long plug into a fused‐silica capillary pre‐filled with phosphate buffer containing 3.0 mol/L of 1‐butyl‐3‐methylimidazolium bromide (BMIMBr). Using AFMC, the analytes were prepared in BMIMBr micellar matrix and hydrodynamically injected into the phosphate buffer without IL micelles. The conductivity ratio between BGE and sample (γ, BGE/sample) was optimized to be 3.0 in sweeping‐MEKC and 0.33 in AFMC resulting the adequate separation of analytes within 4.0 min. To reduce the possibility of BMIMBr adsorption, an appropriate rinsing protocol was used. The limits of detection were calculated as 0.1 ng/mL MTX, 0.05 ng/mL FNA and 0.05 ng/mL FA by sweeping‐MEKC and 0.5 ng/mL MTX, 0.3 ng/mL FNA and 0.3 ng/mL FA by AFMC. The accuracy was tested by recovery in plasma and urine matrices giving values ranging between 90 and 110%. Both stacking and sweeping by BMIMBr could be successfully used for the rapid, selective and sensitive determination of pharmaceuticals in complex matrices due to its fascinating properties, including high conductivity, good thermal stability and ability to form different types of interactions by electrostatic, hydrophobic, hydrogen bonding and π–π interactions. In sweeping‐MEKC, the using of BMIMBr enhanced the γ factor, k retention factor and the injected amount of sample. Consequently, this technique offers particular potential for higher sensitivity by giving 22‐ and 5‐fold sensitivity enhancement factors (SEFs) of MTX compared to CZE and AFMC, respectively.     

Synthesis of arylnaphthalene lignan scaffold by gold-catalyzed intramolecular sequential electrophilic addition and benzannulation

An intramolecular approach to generate compounds containing an arylnaphthalene lignan scaffold in high yields is presented. It involves a sequential intramolecular electrophilic attack of carbonyl on arylalkyne followed by benzannulation catalyzed by gold salt. AuCl(3) in combination with AgSbF(6) works better to effect this transformation. Selected products have been converted into arylnaphthalene lactone natural products such as justicidin E, taiwanin C, and retrojusticidin B.