Sensitivity enhancement of CE and CE-MS for the analysis of peptides by a dynamic pH junction

An analytical method of CE-MS and CE with an online preconcentration technique induced by a dynamic pH junction, addition of organic solvent and large volume injection was developed for sensitive determination of peptides in biological samples. Leucine enkephalin, methionine enkephalin, dynorphin A, β-endorphin and angiotensin II were used as model peptides. The optimal online preconcentration conditions were obtained at a sample matrix consisting of 100?mM borate buffer (pH 10.0) with 50% v/v acetonitrile and a BGE containing 1?M formic acid at pH 2.0, along with a 25-cm injection length. Under the optimized conditions, a 4.0×10(3)-1.1×10(4)-fold increase in peak intensity was achieved without degrading the peak shape. This online preconcentration method was applied to analyze the intracellular angiotensin II within the peptides extracted from HL1 cells and approximately increase of 1×10(4)-fold sensitivity was achieved compared to normal condition. Thus, the developed method could be applied to the analysis of various peptides for peptidomics study in biological samples.     

Synthesis and solution properties of a pH‐responsive cyclopolymer of zwitterionic ethyl 3‐(N,N‐diallylammonio)propanephosphonate

The zwitterionic monomer, ethyl 3‐(N,N‐diallylammonio)propanephosphonate, was cyclopolymerized in aqueous solutions using t‐butylhydroperoxide or ammonium persulfate as initiators to afford a polyphosphonobetaine (PPB). The protonation of P(?O)OEtO^– and deprotonation of ? NH⁺ groups in PPB by HCl and NaOH, gave the corresponding cationic polyphosphononic acid (CPP) and anionic polyphosphonate (APP). The presence of two pH‐responsive functionalities in APP has led to establish the equilibria: APP ? PPB ? CPP, the position of which very much dictates the viscosity behavior of its aqueous solution. The PPB demonstrated “antipolyelectrolyte” viscosity behavior; however, in contrast to many polycarbo‐ and polysulfo‐betaines, it was found to be soluble in salt‐free water as well as in salt‐added solutions. Basicity constant (K₁) of the amine group in APP, as determined by potentiometric technique, were found to be “apparent,” and as such followed the modified Henderson‐Hasselbalch equation. The study demonstrated a correlation between the basicity constants and viscosity values. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Photoredox reactions of Cr(III) mixed-ligand complexes

Irradiation of chromium(III) complexes with oxalate and pyridinedicarboxylate ligands (pda = 2,3-, 2,4-, or 2,5-dicarboxylate) leads to diverse behaviors, dictated by light energy, presence of oxygen and the ligand nature. Irradiation within the MC bands is unaffected by O₂ and results in ligand substitution. The LMCT excitation is effective only when oxalate is coordinated to Cr(III); then electron transfer from oxalate to central ion generates an intermediate, consisted of a Cr(II)species and the C₂O₄^? radicals. The species undergo fast redox reactions dependent on the presence of O₂ and the pda ligand.(1) In anoxic medium the fast outersphere electron transfer from Cr(II) to solvent, generates hydrated electrons and re-oxidizes the chromium centre to Cr^III. Then geminate recombination regenerates substrate, whereas competitive release of the C₂O₄^? radical leads to substitution of one oxalate ligand by two water molecules (aquation induced by the LMCT excitation). In the presence of the pda ligand the outersphere electron transfer is accompanied by the innersphere CT, generating Cr(III) coordinated to two radical ligands: C₂O₄^? and pda^3?; the intermediate releases also e_aq^?, but this reaction is slower than that of the homoleptic oxalate complex. Hydrated electrons are scavenged also by the released radicals. All these processes are completed within microseconds and in consequence, the Cr(III) complexes irradiated in deoxygenated solutions are insensitive to subsequent oxygenation.(2) When UV-irradiation is carried out in oxygenated medium reaction of Cr(II) species with molecular oxygen competes with the outer- or inner electron transfer observed in anoxic medium. Both these pathways result in generation of chromate(VI). Quantum yield of the Cr(VI) production is sensitive to the presence and structure of pda ligand, decreasing within the series 2,3-pda > 2,4-pda > 2,5-pda.     

Structural properties of trans‐cyclohexane‐1,2‐diamine complexes of copper(II) and zinc(II) acesulfamates

The title compounds, trans‐bis(trans‐cyclohexane‐1,2‐diamine)bis(6‐methyl‐2,2,4‐trioxo‐3,4‐dihydro‐1,2,3‐oxathiazin‐3‐ido)copper(II), [Cu(C₄H₄NO₄S)₂(C₆H₁₄N₂)₂], (I), and trans‐diaquabis(cyclohexane‐1,2‐diamine)zinc(II) 6‐methyl‐2,2,4‐trioxo‐3,4‐dihydro‐1,2,3‐oxathiazin‐3‐ide dihydrate, [Zn(C₆H₁₄N₂)₂(H₂O)₂](C₄H₄NO₄S)₂·2H₂O, (II), are two‐dimensional hydrogen‐bonded supramolecular complexes. In (I), the Cu^II ion resides on a centre of symmetry in a neutral complex, in a tetragonally distorted octahedral coordination environment comprising four amine N atoms from cyclohexane‐1,2‐diamine ligands and two N atoms of two acesulfamate ligands. Intermolecular N—H...O and C—H...O hydrogen bonds produce R₂²(12) motif rings which lead to two‐dimensional polymeric networks. In contrast, the Zn^II ion in (II) resides on a centre of symmetry in a complex dication with a less distorted octahedral coordination environment comprising four amine N atoms from cyclohexane‐1,2‐diamine ligands and two O atoms from aqua ligands. In (II), an extensive two‐dimensional network of N—H...O, O—H...O and C—H...O hydrogen bonds includes R₂¹(6) and R₄⁴(16) motif rings.     

Separation and identification of volatile compounds from liquid cultures of Trichoderma harzianum by GC-MS using three different capillary columns

A simple, fast, repeatable and less laborious sample preparation protocol was developed and applied for the analysis of biocontrol fungus Trichoderma harzianum strain FA1132 by using gas chromatography-mass spectrometry. The match factors for sample spectra with respect to the mass spectra library of fungal volatile compounds were determined and used to study the complex hydrocarbons and other volatile compounds, which were separated by using different capillary columns with nonpolar, medium polar and high polar stationary phases. To date, more than 278 volatile compounds (with spectral match factor at least 90%) such as normal saturated hydrocarbons (C7-C30), cyclohexane, cyclopentane, fatty acids, alcohols, esters, sulfur-containing compounds, simple pyrane and benzene derivatives have been identified. Most of these compounds have not previously been reported. The method described in this paper is a more convenient research tool for the detection of volatile compounds from the cultures of T. harzianum.     

Chemical-effect variation of Kβ/Kα X-ray intensity ratios in 3d elements

Chemical effects on Kβ/Kα X-ray intensity ratios for some Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn compounds are studied experimentally. The X-ray spectra were measured by using a Si (Li) solid state detector with high resolution. The vacancies were produced by heavily filtered ²⁴¹Am gamma rays. It is found that the Kβ/Kα X-ray intensity ratios measured with compounds deviated up to 43% from the corresponding values of the pure elements. The values for pure elements are compared with the other experimental and with theoretical values.     

1‐Methyl‐1H‐imidazo[4,5‐f]quinolin‐6‐ium chloride monohydrate

The title compound, C₁₁H₁₀N₃⁺·Cl^?·H₂O, belongs to the N1‐methyl‐substituted imidazo­[4,5‐f]­quinoline family, in which the heterocyclic ring is protonated at the pyridine rather than at the imidazole N atom. The mol­ecule as a whole is almost exactly planar. The molecular structure has been compared with that of the 2‐amino analogue described in the literature, and it was found that the extra amino group of the latter is involved in conjugation with the adjacent double bond, i.e. the conjugation does not extend over the entire heterocyclic system. The cation of the title compound forms a strong hydrogen bond with the Cl^? anion and the anions are interconnected by the water solvent mol­ecule.     

Composition and in vitro antibacterial activity of essential oils from four Satureja species growing in Iran

The composition and in?vitro antibacterial activity of essential oils from four Satureja species (S. bachtiarica, S. khuzistanica, S. mutica and S. rechingeri) growing in Iran were determined. According to the results of GC-FID and GC-MS analysis, all oil samples were principally composed of phenolic constituents (carvacrol and/or thymol) with the percentages ranging from 41.2% (S. bachtiarica) to 77.7% (S. rechingeri). Determining antibacterial activities by the disc diffusion method against two Gram-positive and two Gram-negative bacteria revealed the maximum activity against Bacillus cereus with a range of minimum inhibitory concentration values from 0.25 to 1?mg?mL(-1) and minimum bactericidal concentration values from 0.5 to 1?mg?mL(-1). The oils of S. khuzistanica and S. rechingeri appeared to be more active in general than those of other species. In conclusion, the essential oils of studied Satureja species have the potential to be considered as alternatives for synthetic food preservatives.