Separation of B6 vitamers with micellar liquid chromatography using UV and electrochemical detection

Separation of six vitamers of vitamin B6 was performed by RP-HPLC using micellar mobile phase, UV and electrochemical detection. Effect of temperature, type and amount of organic modifier in mobile phase on efficiency and asymmetry factor showed that, the appropriate conditions were temperature of 35 degrees C and 3.0-5.0% (v/v) 1-butanol in mobile phase. Variations of selectivity factor versus 1-butanol concentration, pH of mobile phase, and SDS concentration was investigated and the following optimized conditions were selected for the separation: 3.0% (v/v) 1-butanol, pH=5.5 and 65 mM SDS in mobile phase. Electrochemical behavior of vitamers in optimized mobile phase was investigated using cyclic voltammetry, and potential of +1.2 V versus Ag/AgCl(Sat.) was chose as working potential. Finally, separation of B6 vitamers using UV detection at 254 nm and electrochemical detection at +1.2 V was compared.     

Development of an optical chemical sensor based on 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol in Nafion for determination of nickel ion

An optical chemical sensor based on immobilization of 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol (Br-PADAP) in Nafion membrane is described. The membranes were cast onto glass substrates and were used for the determination of nickel in aqueous solutions by spectrophotometry. The sensor system is highly transparent, mechanically stable and showed no evidence of reagent leaching. The influence of several parameters such as pH, ligand concentration, and type and concentration of regenerating solution were optimized. The sensor system showed good sensitivity in the range 0.5-20 μg ml⁻¹ with a detection limit of 0.3 μg ml⁻¹ Ni(II). The sensor has been incorporated into a home-made flow-through cell for determination of nickel in flowing streams with improved sensitivity, precision and detection limit. The calibration curve in the flow system was linear in the range 0.1-16 μg ml⁻¹ with a detection limit of 0.07 μg ml⁻¹. The sensor is easily regenerated by dilute nitric acid solution. The proposed method was successfully applied to the determination of nickel content in vegetable oil and chocolate samples and the results were compared with those obtained using atomic absorption spectrometry.     

Green Oxidations. Manganese(II) Sulfate Aided Oxidations of Organic Compounds by Potassium Permanganate

Summary. The oxidation of arenes and sulfides by potassium permanganate was accomplished in good yields under solvent free and heterogeneous conditions when manganese(II) sulfate is used as a solid support. After extraction of the organic products, the inorganic products can be reoxidized to permanganate. This result is important because it provides an approach to oxidation reactions that is, in theory, infinitely sustainable.     

Thermodynamic Properties of Aqueous Glucose–Urea–Salt Systems

In this work, the thermodynamic behavior of aqueous solutions containing the solutes NaCl, glucose, and/or urea is investigated. These substances are vital components for living bodies and further they are main components of blood serum. Osmotic coefficients were determined by cryoscopic measurements in single-solute and multi-solute aqueous solutions containing salts (NaCl, KCl, CaCl₂), glucose, and/or urea. The results show that NaCl determines the osmotic coefficients in the urea/glucose/NaCl/water system. Investigation of the effect of different salts on osmotic coefficients revealed ion-specific effects. At physiologically important solute concentrations in typical blood serum solutions, the osmotic coefficients were found to be in the range of 0.90–0.93. In a second step, the state of water in different glucose/salt/water and urea/salt/water systems was investigated. Depending on the kind of salt, the chemical potential of water in urea/salt/water is either higher or lower than in glucose/salt/water systems at equal nonelectrolyte concentrations. This result was found to be independent of the salt molality. Finally, the investigated systems were modeled with the Pitzer model and the ePC-SAFT equation of state, which allowed predicting of the properties of these multi-solute aqueous solutions.     

A green,efficient and recyclable poly(4-vinylpyridine)-supported copper iodide catalyst for the synthesis of coumarin derivatives under solvent-free conditions

Poly(4-vinylpyridine)-supported copper iodide is reported as a green, efficient and recyclable catalyst for the synthesis of coumarin derivatives by the Pechmann reaction under solvent-free conditions. This catalyst can be recovered by simple filtration and recycled up to eight consecutive runs without any loss of their efficiency.     

Luminescent mononuclear and dinuclear cycloplatinated (II) complexes comprising azide and phosphine ancillary ligands

A new series of cycloplatinated (II) complexes with general formulas of [Pt (bhq)(N₃)(P)] [bhq = deprotonated 7,8‐benzo[h]quinoline, P = triphenyl phosphine (PPh₃) and methyldiphenyl phosphine], [Pt (bhq)(P^P)]N₃ [P^P = 1,1‐bis (diphenylphosphino)methane (dppm) and 1,2‐bis (diphenylphosphino)ethane] and [Pt₂(bhq)₂(μ‐P^P)(N₃)₂] [P^P = dppm and 1,2‐bis (diphenylphosphino)acetylene] is reported in this investigation. A combination of azide (N₃^?) and phosphine (monodentate and bidentate) was used as ancillary ligands to study their influences on the chromophoric cyclometalated ligand. All complexes were characterized by nuclear magnetic resonance spectroscopy. To confirm the presence of the N₃^? ligand directly connected to the platinum center, complex [Pt (bhq)(N₃)(PPh₃)] was further characterized by single‐crystal X‐ray crystallography. The photophysical properties of the new products were studied by UV–Vis spectroscopy in CH₂Cl₂ and photoluminescence spectroscopy in solid state (298 or 77 K) and in solution (77 K). Using density functional theory calculations, it was proved that, in addition to intraligand charge‐transfer (ILCT) and metal‐to‐ligand charge‐transfer (MLCT) transitions, the L′LCT (L′ = N₃, L = C^N) electronic transition has a remarkable contribution in low energy bands of the absorption spectra (for complexes [Pt (bhq)(N₃)(P)] and [Pt₂(bhq)₂(μ‐P^P)(N₃)₂]). It is indicative of the determining role of the N₃^? ligand in electronic transitions of these complexes, specifically in the low energy region. In this regard, the photoluminescence studies indicated that the emissions in such complexes originate from a mixed ³ILCT/³MLCT (intramolecular) and also from aggregations (intermolecular).     

N‐Inversion in N‐phenyloxaziridine: substituent and solvent effects via density functional theory

In this work, using density functional theory, the kinetic effects of the substitution of a t‐butyl group and\or the incorporation of an oxygen atom, and both, at the aziridine ring moiety were investigated for N‐inversion in N‐phenylaziridine. Then, for N‐inversion in 3‐t‐butyl‐N‐phenyloxaziridine, the kinetic Hammett substituent effects were studied using the different para‐substituted groups on the N‐phenyl ring moiety. The natural bond orbital (NBO) study was the last case in this work. The calculations were performed in the gas phase and solution (in carbon tetrachloride and dichloromethane). The incorporation of an oxygen atom in the aziridine ring strongly weakens the N‐inversion process. In addition, while both t‐butyl substituent and solvent slightly reinforce the N‐inversion of N‐phenyloxaziridine, in N‐phenylaziridine, they decrease the N‐inversion rate to some extent. In both phases, more pronounced in solution and especially in dichloromethane, and in agreement with the NBO results, the electron‐withdrawing groups on para position of the N‐phenyl ring strongly increase the rate of N‐inversion of 3‐t‐butyl‐N‐phenyloxaziridine molecule.     

Design and identification of nano-Mg-[4-methoxy phenyl-salicylaldimine–methyl-pyranopyrzole] Cl2 and its catalytic application on the preparation of 1-(α-aminoalkyl)-2-naphthols

Nano-Mg- [4-methoxy phenylsalicylaldiminemethylpyranopyrazole]Cl₂ (nano-[Mg-4MSMP]Cl₂) as a nano-Schiff base complex was prepared and fully characterized using some various techniques including fourier transform infrared spectroscopy (FT-IR), energy-dispersive x-ray spectroscopy (EDS), X-ray diffraction (XRD), thermal gravimetric analysis (TGA), differential thermal gravimetric analysis (DTA), mass spectroscopy (MS) and scanning electron microscopy (SEM). Nano-[Mg-4MSMP]Cl₂ was successfully used as an efficient catalyst for the preparation of some 1-(α-aminoalkyl) -2 -naphthols.     

Polyelectrolyte complexation between poly(methacrylic acid,sodium salt) and poly(diallyldimethylammonium chloride) or poly[2‐(methacryloyloxyethyl) trimethylammonium chloride]

Polyelectrolyte complexes between poly(methacrylic acid, sodium salt) and poly(diallyldimethylammonium chloride) (PDADMAC) or poly[2‐(methacryloyloxyethyl)trimethylammonium chloride] (PMOETAC) form gels, liquid phases, or soluble complexes depending on charge ratio, total polymer loading, polymer molecular weight, and ionic strength. Increasing the ionic strength of the medium led most polyelectrolyte pairs to transition from gel through liquid complexes (complex coacervate) to soluble complexes. These transitions shift to higher ionic strengths for higher molecular weight polymers, as well as for PMOETAC compared to PDADMAC. The complex phases swelled with increasing polymer loading, ultimately merging with the supernatant phase at a critical polymer loading. The isolated liquid complex phases below and above this critical loading were temperature‐sensitive, showing cloud points followed by macroscopic phase separation upon heating. Incorporating 5 mol % lauryl methacrylate into the polyanion led to increased complex yield with PDADMAC, and increased resistance to ionic strength. In contrast, incorporating 30 mol % of oligo(ethylene glycol) methacrylate into the polyanion led to decreased complex yield, and to lower resistance to ionic strength. Two polyelectrolyte systems that produced liquid complexes were used to encapsulate hydrophobic oils, and in one case were used to demonstrate the feasibility of crosslinking the resulting capsule walls. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4129–4143, 2007     

Fuzzy chance-constrained data envelopment analysis: a structured literature review,current trends,and future directions

Fuzzy Optimization and Decision Making - Fuzzy data envelopment analysis (FDEA) is one of the most applicable approaches for performance assessment of peer decision making units under ambiguity...