Theoretical studies of carbocations in ion pairs. 8. Search for anchimeric assistance in the ionization of 2-butyl cation precursors

The structures of carbocations formed in the ionization of 2-butyl precursors were investigated by high level ab initio MO calculations on the reaction of 2-butyl fluoride (1) with borane, which gives a C4H9+ cation paired with trihydrofluoroborate (FBH3-, A). Two conformations of the "open," secondary cation (2) in the ion pair resulted from two conformations of 1, with F gauche and trans to C4 (2-g and 2-t, respectively). No anchimeric assistance by hydrogen (in 1-g) or methyl (in 1-t) was evidenced. In fact, attempts at optimizing the geometry of the H-bridged (3) and methyl-bridged (6) cations at short interionic distances (d) led to the corresponding conformations of 2. Upon ion separation, proton transfer from 2 to the anion occurred at intermediate interionic distances, consonant with experimental observations in trifluoroacetic acid. Elimination was prevented by addition of a lithium cation to the ion pair, i.e., running computations on triple ions (2.A.Li+). Cation 6 became an energy minimum beyond d = 2.5 A and 3 beyond 2.8 A. Cation 2-g was still the most stable isomer at d = 3.2 A, which was greater than the interionic distance in the crystals of the isomeric tert-butyl cation salts (3-3.1 A). Thus, spectral determinations of 2-butyl cations in the solid state should be interpreted with 2-g as the main component of the ion mixture. When the ions became separated (d >/= 4 A), only the bridged ions were energy minima. In this process, bridging did not occur opposite to the leaving group to assist the ionization, but on the same side with it, being controlled by the electrostatic interaction with the anion, as it departed from the vicinity of the cation. Such behavior was also noted in the ionization of the 3-methyl-2-butyl homolog.     

Per-O-methylation of neutral carbohydrates directly from aqueous samples for gas chromatography and mass spectrometry analysis

Per-O-methylation of neutral carbohydrates in one step by adding dimethyl sulfoxide, powdered sodium hydroxide, and methyl iodide directly to aqueous sample is described. The influence of the water on the methylation reaction is investigated. Solid powdered sodium hydroxide is very hygroscopic and can scavenge the water from sample if an additional excess of sodium hydroxide is added. The degree of per-O-methylation of carbohydrates is checked by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Gas chromatography-mass spectrometry analysis of mono- and disaccharides from grape juice is presented.     

L/E-flatness of the electron-like event ratio, in Super-Kamiokande and a degeneracy, in neutrino masses

We show that the L/E-flatness of the electron-like event ratio in the Super-Kamiokande atmospheric neutrino data implies the equality of the expectation values for the muon and tau neutrino masses. We establish this result by obtaining a set of three constraints on the neutrino-oscillation mixing matrix as contained in the indicated flatness. The resulting 3×3 neutrino-oscillation matrix depends only on one angle. A remarkable result that follows directly from this matrix is the consistency between the mixing angles observed by LSND and Super-Kamiokande.     

Characterization of self-assembled monolayers (SAMs) on silicon substrate comparative with polymer substrate for Escherichia coli O157:H7 detection

This article presents the characterization of two substrates, silicon and polymer coated with gold, that are functionalized by mixed self-assembled monolayers (SAMs) in order to efficiently immobilize the anti-Escherichia coli O157:H7 polyclonal purified antibody.A biosurface functionalized by SAMs (self-assembled monolayers) technique has been developed. Immobilization of goat anti-E. coli O157:H7 antibody was performed by covalently bonding of thiolate mixed self-assembled monolayers (SAMs) realized on two substrates: polymer coated with gold and silicon coated with gold. The F(ab′)₂ fragments of the antibodies have been used for eliminating nonspecific bindings between the Fc portions of antibodies and the Fc receptor on cells. The properties of the monolayers and the biofilm formatted with attached antibody molecules were analyzed at each step using infrared spectroscopy (FTIR-ATR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and cyclic voltammetry (CV). In our study the gold-coated silicon substrates approach yielded the best results.These experimental results revealed the necessity to investigate each stage of the immobilization process taking into account in the same time the factors that influence the chemistry of the surface and the further interactions as well and also provide a solid basis for further studies aiming at elaborating sensitive and specific immunosensor or a microarray for the detection of E. coli O157:H7.     

Shape tailoring of hexagonally ordered triangular gold nanoparticles with nanosecond-pulsed laser light

In this contribution recent results on selective and precise tailoring of triangular gold nanoparticles (NPs) using ns-pulsed laser light are presented. The NPs were prepared by nanosphere lithography and subsequently tailored with ns-pulsed laser light using different fluences and wavelengths. The method is based on the size and shape dependent localized surface plasmon polariton resonance (SPR) of the NPs. We will demonstrate that the gap size between triangular NPs can be tuned from approximately 102±14 nm to 122±11 nm, due to a shape change of the NP from triangular to oblate. These morphological changes are accompanied by a significant shift of the surface plasmon resonance from λ_SPR=730 nm to λ_SPR=680 nm. Most importantly if the laser wavelength is chosen such that the dipolar SPR is excited, the hexagonal order of the NPs remains intact after irradiation, in contrast to excitation via the quadrupole SPR or within the interband transition. A tuneable gap size and the conservation of the hexagonal order of the NP array is the precondition for applications, where the NPs should serve as anchor points, e.g. for functional molecular nanowires, which can be used to utilize molecular devices.     

Investigation of nanostructured Fe3O4 polypyrrole core-shell composites by X-ray absorbtion spectroscopy and X-ray diffraction using synchrotron radiation

In this article, we focus on the structural peculiarities of nanosized Fe₃O₄ in the core-shell nanocomposites obtained by polymerization of conducting polypyrrole shell around Fe₃O₄ nanoparticles. The local structure of Fe atoms was determined from the Extended X-ray Absorption Fine Structure analysis using our own package computer programs. An X-ray diffraction method that is capable to determine average particle size, microstrains, as the particle size distribution of Fe₃O₄ nanoparticles is presented. The method is based on the Fourier analysis of a single X-ray diffraction profile using a new fitting method based on the generalized Fermi function facilities. The crystallites size obtained by X-ray diffraction spectra analysis was estimated between 3.2 and 10.3 nm. Significant changes in the first and the second Fe coordination shell in comparison with standard bulk were observed. The global and local structure of the nanosized Fe₃O₄ are correlated with the synthesis conditions of the core-shell polypyrrole nanocomposites.     

HPTLC Quantification of Some Flavonoids in Extracts of Satureja hortensis L. Obtained by Use of Different Techniques

JPC – Journal of Planar Chromatography – Modern TLC - A study of quantitative analysis of some flavonoids in Satureja hortensis L. extracts is presented. The HPTLC analyses were...     

Thermal decomposition of some biologically active complexes of ruthenium (III) with quinolone derivatives

A series of new complexes with mixed ligands of the type RuL₂(DMSO) _m Cl₃·nH₂O ((1) L: norfloxacin (nf), m = 1, n = 1; (2) L: ciprofloxacin (cp), m = 2, n = 2; (3) L: ofloxacin (of), m = 1, n = 1; (4) L: enrofloxacin (enro), m = 0.5, n = 4; DMSO: dimethylsulfoxide) were synthesised and characterised by chemical analysis and IR data. In all complexes both fluoroquinolone derivative and DMSO act as unidentate. The thermal behaviour steps were investigated in synthetic air flow. The thermal transformations are complex processes according to TG and DTG curves including dehydration, quinolone derivative and DMSO degradation respectively. The final product of decomposition is ruthenium (IV) oxide.     

Spectrophotometric Characteristics of New Pyridylindolizine Derivatives Solutions

Three new pyridylindolizine derivatives, 1, 2, 3-tricarbometoxi-7-(4-pyridyl)-pyrrolo[1, 2-a]pyridine (I), 1,2-dicarboethoxy-3-(4-bromobenzoyl)-7-(4-pyridyl)-pyrrolo[1,2-a]pyridine (II) and its isomer 1,2-dicarboethoxy-3- (4-bromobenzoyl) -5- (2-pyridyl) -pyrrolo[1, 2-a]pyridine (III) have been investigated in different solutions by UV-VIS absorption, steady-state, and time-resolved fluorescence methods. The effects of the substituent and solvent on the spectroscopic properties have been demonstrated. The fluorescence decay data could be fitted to a single-exponential function. The lifetime values are higher in protic polar than in aprotic apolar solvents for compound I. In the case of compounds II and III the fluorescence intensities and lifetimes are very low, with the exception of III in aprotic solvents. The absorption and fluorescence properties of the compounds showed a solvent dependence.     

Synthesis,characterization, and cytotoxicity evaluation of high-magnetization multifunctional nanoclusters

The paper presents the synthesis, characterization, and in vitro cytotoxicity tests of Fe₃O₄ magnetic nanoclusters coated with ethylenediaminetetraacetic acid disodium salt (EDTA). Electron microscopy analysis (SEM) evidences that magnetite nanoparticles are closely packed into the clusters stabilized with EDTA with well-defined near spherical shapes and sizes in the range 100–200 nm. From XRD measurements, we determined the mean size of the crystallites inside the magnetic cluster about 36 nm. The saturation magnetization determined for the magnetic clusters stabilized with EDTA has high value, about 81.7 emu/g at 300 K. X-ray photoelectron spectroscopy has been used to determine both the elemental and chemical structure of the magnetic cluster surface. In vitro studies have shown that the magnetic clusters at low doses did not induce toxicity on human umbilical vein endothelial cells or lesions of the cell membrane. In contrast, at high doses, the magnetic clusters increased the lipid peroxidation and reduced the leakage of a cytoplasmic enzyme, lactate dehydrogenase (LDH), in parallel with increasing the antioxidant defense.

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Graphical abstract SEM images of EDTA-coated magnetic clusters (MCs) and the HUVEC viability at different MC doses