Highly selective enrichment of phosphopeptides using poly(dibenzo‐18‐crown‐6) as a solid‐phase extraction material

A poly(dibenzo‐18‐crown‐6) was used as a new solid‐phase extraction material for the selective enrichment of phosphopeptides. Isolation of phosphopeptides was achieved based on specific ionic interactions between poly(dibenzo‐18‐crown‐6) and the phosphate group of phosphopeptides. Thus, a method was developed and optimized, including loading, washing and elution steps, for the selective enrichment of phosphopeptides. To assess this potential, tryptic digest of three proteins (α‐ casein, β‐casein and ovalbumin) was applied on poly(dibenzo‐18‐crown‐6). The nonspecific products were removed by centrifugation and washing. The spectrometric analysis was performed using matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. Highly selective enrichment of both mono‐ and multiphosphorylated peptides was achieved using poly(dibenzo‐18‐crown‐6) as solid‐phase extraction material with minimum interference from nonspecific compounds. Furthermore, evaluation of the efficiency of the poly(dibenzo‐18‐crown‐6) was performed by applying the digest of egg white. Finally, quantum mechanical calculations were performed to calculate the binding energies to predict the affinity between poly(dibenzo‐18‐crown‐6) and various ligands. The newly identified solid‐phase extraction material was found to be a highly efficient tool for phosphopeptide recovery from tryptic digest of proteins.     

Different lethal effects by enzyme-generated triplet indole-3-aldehyde in different Escherichia coli strains

Strains of Escherichia coli which lack 4-thiouridine (S4U) exhibit a higher survival rate than their wild-type parents which contain S4U after treatment with enzyme-generated triplet indole-3-aldehyde. In a similar manner to results obtained with monochromatic 334 nm UV light, the survival is related to single-strand breakage of DNA in E. coli containing the pBR 322 plasmid. The effects of the excited states generated by an enzymatic system suggest that S4U is an important chromophore in the lethal effects observed. The results also suggest that the energy transferred from triplet indole-3-aldehyde to S4U may also be passed from S4U of t-RNA to DNA, possibly through a singlet oxygen intermediate generated by excited S4U, resulting in a decrease in the survival rate of E. coli containing S4U. These results emphasize the importance of excited states in biological systems.     

Synthesis,characterization and non-linear optical properties of two mononuclear Cu(II) complexes of 2,6-bis(1-butylbenzimidazol-2-yl)pyridine

Two copper(II) complexes, [Cu(L)(N₃)₂]·MeOH and [Cu(L)(NCS)₂]·MeOH, were prepared and characterized by spectroscopic, analytical, and quantum chemical studies, where L is 2,6-bis(1-butylbenzimidazol-2-yl)pyridine. X-ray quality crystals of [Cu(L)(N₃)₂]·MeOH were obtained by slow evaporation of MeOH solution of the complex. Molecular structure of [Cu(L)(N₃)₂]·MeOH was determined by X-ray crystallography. The asymmetric unit contains one [Cu(L)(N₃)₂] and one MeOH molecule. Cu(II) in [Cu(L)(N₃)₂]·MeOH is five-coordinate, bonded to five nitrogens (three from L and two from two azide anions). Coordination geometry around Cu(II) center is distorted square-pyramidal with τ value of 0.065. Optimized geometries, IR spectra, and non-linear optical properties of the complexes were obtained by computational studies based on density functional theory (DFT) with M062X method. NLO properties of these complexes were investigated computationally and both complexes exhibit better NLO properties than urea.     

Pd(II) complexes of novel phosphine ligands: Synthesis,characterization, and catalytic activities on Heck reaction

Novel phosphine oxides, (((3-methylpyridin-2-yl)amino)methyl)diphenylphosphine oxide (1) and diphenyl((pyrazin-2-ylamino)methyl)phosphine oxide (2), were synthesized and characterized. Phosphines ligands (3 and 4) were obtained by the reduction of 1 and 2 with AlH₃, monitored by ³¹P NMR spectroscopy. Pd(II) complexes of 3 and 4 were synthesized and characterized (5 and 6). The catalytic activity of 5 and 6 was tested on the reaction of styrene with both activated and deactivated aryl bromides in air. The results of the catalytic experiments were discussed through DFT calculations.     

AFM study of micelle chaining in surface films of polystyrene-block-poly(ethylene oxide) stars at the air/water interface

A series of three-arm star block copolymers were examined using atomic force microscopy (AFM). These stars consisted of a polystyrene core composed of ca. 111 styrene units/branch with poly(ethylene oxide) (PEO) chains at the star periphery. Each star contained different amounts of PEO, varying from 107 to 415 ethylene oxide units/branch. The stars were spread as thin films at the air/water interface on a Langmuir trough and transferred onto mica at various surface pressures. Circular domains representing 2D micelle-like aggregated molecules were observed at low pressures. Upon further compression, these domains underwent additional aggregation in a systematic manner, including micellar chaining. At this point, domain area and the number of molecules/domain increased with increasing pressure. In addition, it was found that longer PEO chains led to greater intermolecular separation and less aggregation. These AFM results correspond to attributes seen in the surface pressure-area isotherms of the stars. In addition, they demonstrate the viability of AFM as a quantitative characterization technique.     

Composition of essential oils from <Emphasis Type="Italic">Salvia anatolica</Emphasis>, a new species endemic from Turkey

The component composition of essential oils produced by steam distillation from flower heads, leaves, and stems of Salvia anatolica (Lamiaceae), a recently described new species endemic from Turkey, was studied by GC/FID and GC/MS. A total of 127 volatile components representing 96% of the oil was identified in essential oil from flower heads and leaves. It was found that the principal oil components of flower heads and leaves were α-pinene (10.9%), β-pinene (6.7%), α-copaene (6.3%), heptacosane (6.2%), and hexadecanoic acid (5.0%). A total of 109 volatile compounds representing 87.9% of the oil was characterized in essential oil isolated from stems. The principal oil components of stems were identified as hexadecanoic acid (27.2%), tetradecanoic acid (15.2%), dodecanoic acid (5.5%), and α-copaene (5.0%). __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 552–555, November–December, 2007.     

The use of ab initio quantum molecular self-similarity measures to analyze electronic charge density distributions

Exact quantum molecular overlaplike and Coulomb-like self-similarity measures are studied in a selected series of molecules with the same number of electrons. It is found that quantum molecular overlap self-similarity measures can be used to estimate the concentration of electronic charge in molecules. A good linear relationship between the overlap self-similarity measure and the volume is found for molecules with the same number of electrons when the atoms of the systems being compared belong to the same row of the periodic table. Finally, an upper bound for the quantum molecular overlap self-similarity measure of molecules with a number of electrons up to 54 is given from the atomic quantum self-similarity measures obtained using Slater-type functions. © 1996 John Wiley & Sons, Inc.     

Efficiency of a Liu-type estimator in semiparametric regression models

In this paper we consider the semiparametric regression model, y=Xβ+f+ε. Recently, Hu [11] proposed ridge regression estimator in a semiparametric regression model. We introduce a Liu-type (combined ridge-Stein) estimator (LTE) in a semiparametric regression model. Firstly, Liu-type estimators of both β and f are attained without a restrained design matrix. Secondly, the LTE estimator of β is compared with the two-step estimator in terms of the mean square error. We describe the almost unbiased Liu-type estimator in semiparametric regression models. The almost unbiased Liu-type estimator is compared with the Liu-type estimator in terms of the mean squared error matrix. A numerical example is provided to show the performance of the estimators.     

Stability analysis of asset flow differential equations

I study the stability analysis of the solutions for the dynamical system of nonlinear asset flow differential equations (AFDEs) in three versions. I show that the previous two versions are not structurally stable mathematically because there are infinitely many critical points. It is important to reformulate a problem in order to eliminate any hypersensitivity in the mathematical model. I find that there is no critical point in the new version unless the chronic discount over the past finite time interval is zero.