Determination of tryptophan in raw materials, rat brain and human plasma by RP-HPLC technique

This paper describes tryptophan (TRP) estimation in raw human plasma and rat brain by reversed-phase high-performance liquid chromatography (RP-HPLC). Estimation was carried out on a Purospher STAR C18 column using water-acetonitrile (90:10 v/v, at pH 2.7) mixture at a rate of 1.5 mL/min as mobile phase. Eluents were monitored at 273 nm by an ultraviolet detector. The method was linear (R(2) > 0.999), precise (intra-day and inter-day precision <2%) in the range of 0.25-20 μg/mL. The detection and quantification limits were 0.0144 μg/mL and 0.0437 μg/mL, respectively. In human plasma, Day 1 and Day 2 precision were 0.054-2.29% and 1.66-3.7%; whereas precisions in rat brain were 1.23-2.3% and 0.677-4.2%, respectively. The method was applied to study TRP level in human smokers and in arthritic rat brain. An efficient RP-HPLC method was developed for TRP determination that worked for clinical and research purposes.     

Thermodynamic study of complex formation process of free base meso-tetraphenylporphyrins with dimethyl and dibutyltin(IV) dichloride: a new algorithm for a single thermometric titration

A novel, fast and easy single sample measurement has been developed based upon temperature dependence of equilibrium constant in order to determine the enthalpy and entropy changes of a complexation reaction using spectrophotometric temperature titration. The method can be used in determination of the formation constant and thermodynamic parameters of the solutions that there are difficulties in their titration where volatile compounds are studying. Knowledge of component spectra is not required for the analysis. The formation constants of the interactions of ß-di and tri-brominated meso-tetraphenylporphyrins, and meso-tetrakis(4-methylphenyl) and (4-methoxyphenyl) porphyrins with Me₂SnCl₂ and Bu₂SnCl₂, have been determined in range of 0–25 °C utilizing van’t Hoff relation, mass balance and equilibrium constant equations by an iterative least squares method with ΔH ⁰ as adjustable parameter. The outputs of analysis are the equilibrium constants, ligand and adduct spectral profiles, their concentrations as a function of temperature, the adjusted values of the standard enthalpy ΔH ⁰, and entropy ΔS ⁰ changes. The order of formation constants of the resulting 1:1 complexes decreased with increasing number of bromide substituents and increased with adding methyl and methoxy groups, and vary as H₂T(4-CH₃O)PP > H₂T(4-CH₃)PP > H₂TPP > H₂TPPBr₂ > H₂TPPBr₃ and Me₂SnCl₂ > Bu₂SnCl₂.     

An Ab Initio Study and NBO Analysis of the Stability and Conformational Properties of Hexakis(trimethylelementhyl)benzene (Element = C,Si, Ge,and Sn)

Ab initio molecular orbital and density functional theory were used to investigate energetic and structural properties of the various conformations of hexa-tertbutylbenzene (1), hexakis(trimethylsilyl)benzene (2), hexakis (trimethylgermyl)benzene (3), and hexakis(trimethylstannyl)benzene (4). HF/3-21G//HF/3-21G and B3LYP/3-21G//HF/3-21G results revealed that the Twist-Boat (TB) conformer of compound 1 is more stable than the 1-Chair (C), 1-Boat (B), and 1-Planar (P) conformers. B3LYP/3-21G//HF/3-21G results show that the 1- TB conformer is more stable than 1- C, 1- B, and 1- P conformers of about 1.13, 4.34, and 99.94 kcal mol^?1 , respectively. Contrary to the stability order of compound 1 conformers, the C conformer of compounds 2–4 is more stable than TB, B, and P conformations, as calculated by B3LYP/3-21G//HF/3-21G and HF/3-21G//HF/3-21G levels of theory. The energy gap between the C and P conformers in compounds 1–4 is decreased in the following order: ΔE(4: C, P) < ΔE (3: C, P) < ΔE(2: C, P) < ΔE (1: C, P). This fact can be explained in terms of the increase of C _aromatic -M (M═C, Si, Ge, and Sn) bond lengths and the decrease of steric (van der Waals) repulsions in the previously discussed compounds. For compounds 1–3, the calculations were also performed at the B3LYP/ 6-31G*//HF/3-21G level of theory. However, the comparison showed that the results at B3LYP/3-21G//HF/3-21G methods correlated well with those obtained at the B3LYP/6-31G*// HF/6-31G method. Further, NBO analysis revealed that in compounds 1–4, the resonance energy associated with the σ_M-C1 to σ*_C2-C3 delocalization is 5.20, 9.68, 11.15, and 12.27 kcal mol^?1, respectively. These resonance energy values could explain the easiness of the ring flipping processes of C, B, and TB conformers of compounds 4 to 1. Also, the NBO results showed that by an increase of the σ_M-C1 → σ *_C2-C3 resonance energies in compounds 1–4, the σ_M-C1 bonding orbital occupancies decrease. This fact could fairly explain the increase of the C_aryl-M bond length from compound 1 to 4. The NBO results are also in good agreement with the calculated energy barriers for the ring flipping of the chair conformations in compounds 1–4, as calculated by B3LYP and HF methods.     

Solvent-Free Acetylation of Thiols Under Catalysis of MgBr2·OEt2

Solvent-free protection of aromatic and aliphatic thiols with acetic anhydride was performed at room temperature under trace quantities of magnesium bromide ethyl etherate, affording rapid formation of various thiol esters in excellent yields.     

Synthesis and characterization of A2 + B3 type hyperbranched aromatic-aliphatic polyester with carboxyl end groups

New types of carboxyl-terminated hyperbranched polyesters (HBPEs) with aromatic-aliphatic structure were synthesized by single step-melt polycondensation of adipic acid (as A2 monomer) and phloroglucinol (as B3 monomer) as a core via A₂ + B₃ approach, at three different monomer mole ratios (A₂/B₃ = 1: 1, 1.5: 1, 2: 1, respectively). FTIR spectroscopy indicated that the polymers contained hydroxyl groups, ester bonds, benzene ring, methyl and methylene groups, which were in agreement with the expected HBPEs. The HBPEs have inherent viscosities about 0.24 to 0.27 dL/g. The degree of branching of the HBPEs was estimated to be 0.45–0.49% by ¹H-NMR and ¹³C-NMR measurements. The melting temperature of HBPE-1, HBPE-2 and HBPE-3 were 154, 155 and 160°C respectively measured by differential scanning calorimetry (DSC). The synthesized polymers were thermally stable; the thermogravimetric analysis (TGA) measurement revealed that HBPEs had 10% weight loss at 310°C in nitrogen.     

Microfunnel‐filter‐based emulsification microextraction followed by gas chromatography for simple determination of organophosphorus pesticides in environmental water samples

A simple and fast method named microfunnel‐filter‐based emulsification microextraction is introduced for an efficient determination of some organophosphorus pesticides including diazinon, malathion, and chlorpyrifos in the environmental samples including the river, sea, and well water. This method is based upon the dispersion of a low‐toxicity organic solvent (dihexyl ether), as the extractant, in a high volume of an aqueous sample solution (45 mL). It is implemented without a centrifugation step, and using a syringe filter and a micro‐funnel, the phase separation and transfer of the enriched analytes to the gas chromatograph are simply achieved. By filtration of the extractant phase, a suitable sample clean‐up is obtained, and the total extraction time is just a few minutes. The factors influencing the extraction efficiency are optimized, and under the optimal conditions, the proposed method provides a good linearity (in the range of 15–1500 ng/mL (R² > 0.996). A high enrichment factor is obtained (in the range of 306–342), and the method provides low limits of detection and quantification (in the ranges of 4–8 and 15–25 ng/mL, respectively).     

A New and Simple Electrocatalyst for Formaldehyde Oxidation; Nickel/poly(o‐Anisidine)/Film Modified Ionic Liquid Carbon Paste Electrode

In present work, the ionic liquid, 1‐butyl‐3‐methylimidazolium bis (trifluoromethylsulfonyl) imide was incorporated in the carbon paste electrode as the binder (IL‐CPE). O‐anisidine (OA) monomer is electropolymerized in the presence of an aqueous acidic solution onto IL‐CPE (POA/IL‐CPE). The as‐prepared substrate is used as a porous matrix for dispersion of Ni(II) ions by immersing the modified electrode in a nickel(II) nitrite solution. The modified electrodes are characterized by scanning electron microscopy (SEM) and electrochemical methods. The POA/IL‐CPE was applied successfully to highly efficient (current density of 18.2 mA cm^?2) electrocatalytic oxidation of formaldehyde in alkaline medium. Finally, the rate constant for chemical reaction between formaldehyde and redox sites of the electrode was calculated.     

Diammonium Hydrogen Phosphate: An Efficient and Versatile Catalyst for the One‐Pot Synthesis of Tetrahydrobenzo[b]pyran Derivatives in Aqueous Media

Diammonium hydrogen phosphate was used as a mild, efficient, neutral, and cheap catalyst for the synthesis of various 4H‐benzo[b]pyran derivatives via a one‐pot, three‐component condensation of aromatic aldehydes, active methylene compounds, and dimedone in aqueous media.