Recognition of chiral catechols using oxo-titanium phthalocyanine

Oxo-titanium phthalocyanine (TiOPc) derivatives of catechin and hematoxylin (natural ortho-diol type chiral compounds) have been prepared and characterized by spectral and chromatographic techniques. It is demonstrated that the TiOPc unit is an excellent template for chiral recognition through its isolated Q-transitions. The formation of a helical dimeric complex with hematoxylin induces strong CD-activity in the Q-band region. Ab initio geometry optimizations were combined with a Kuhn-Kirkwood coupled-oscillator mechanism to obtain the absolute configuration of hematoxylin. In addition, it is shown that the described chiroptical recognition method is sensitive to slight conformational changes.     

Gilmaniellin and Dechlorogilmaniellin,Two Novel Dimeric Oxaphenalenones

The structure and configuration of gilmaniellin, a metabolite of Gilmaniella humicola BARRON , has been shown to be 2 by X-ray analysis. By comparison of spectral data structure 1 has been assigned to dechlorogilmaniellin.     

On the Pauling electronegativity scales—I

It is shown that the Pauling electronegativity scale χ is closely related to the electrostatic potential near the physical meaningful boundary between the core and valence regions in an atom, and is well reproduced by the relationship:

where N_ν is the valence electron number and the factor f(n) is empirically given by

n being the periodic number.     

Flow amperometric detection of indigo for enzyme-linked immunosorbent assays with use of screen-printed electrodes

A simple and automated methodology for a sensitive electrochemical detection of enzyme immunoassays that employ alkaline phosphatase (AP) as label has been developed. A flow injection system with programmable pump, valve and cell functions, amperometric detection of indigo and screen-printed electrodes (SPEs) are responsible for the advantages of this methodology. Amperometric detection at a low potential of indigo, the product of the enzymatic hydrolysis of the substrate 3-indoxyl phosphate (IP), is combined with a flow injection system. This incorporates in the flow cell a disposable screen-printed board provided with a graphite working electrode. No electrode pretreatment is necessary to obtain reproducible signals. The system was applied to the determination by an enzyme-linked immunosorbent assays (ELISA) of pneumolysin (PLY), a toxin related to respiratory infections. Linear calibration curves for low and high concentration ranges were obtained. These were also performed in a proteic matrix and linearity was also obtained.     

Immobilization of a Monolayer of Bovine Serum Albumin on Gold Nanoparticles for Stereo‐specified Recognition of Dansyl‐norvaline

The assembly strategy to prepare a monolayer of bovine serum albumin on the surface of silica gel supported gold nanoparticles is described. The stereo‐specific recognition ability of this material was evaluated by enantioresolution of Dansyl‐norvaline. For enantiomeric separation, the influences of buffer concentration and the concentration of organic modifier on the separation performance were investigated. A better separation in terms of enantioresolution and peak shape was found with the phosphate concentration at 30 mM. Moreover, the peak shape and resolution can be improved by the addition of methanol solution. Enantioresolution of Dansyl‐norvaline was obtained from this material at optimized conditions. It appears that the immobilization of a monolayer of bovine serum albumin on gold nanoparticles as the chiral selector of Dansyl‐derivative amino acid is promising.     

Metallic copper for the standardization of edta solution

The standardization of EDTA solution against metallic copper as primary standard is studied. Six indicators were examined; titration with PAN as indicator at pH 6 is recommended.     

Deuterium isotope effects on hydrophobic interactions: the importance of dispersion interactions in the hydrophobic phase

Hydrogen/deuterium isotope effects on hydrophobic binding were examined by means of reversed-phase chromatographic separation of protiated and deuterated isotopologue pairs for a set of 10 nonpolar and low-polarity compounds with 10 stationary phases having alkyl and aryl groups bonded to the silica surface. It was found that protiated compounds bind to nonpolar moieties attached to silica more strongly than deuterated ones, demonstrating that the CH/CD bonds of the solutes are weakened or have less restricted motions when bound in the stationary phase compared with the aqueous solvent (mobile phase). The interactions responsible for binding have been further characterized by studies of the effects of changes in mobile phase composition, temperature dependence of binding, and QSRR (quantitative structure-chromatographic retention relationship) analysis, demonstrating the importance of enthalpic effects in binding and differentiation between the isotopologues. To explain our results showing the active role of the hydrophobic (stationary) phase we propose a plausible model that includes specific contributions from aromatic edge-to-face attractive interactions and attractive interactions of aliphatic groups with the pi clouds of aromatic groups present as the solute or in the stationary phase.     

Monolithic silica columns with various skeleton sizes and through-pore sizes for capillary liquid chromatography

Reduction of through-pore size and skeleton size of a monolithic silica column was attempted to provide high separation efficiency in a short time. Monolithic silica columns were prepared to have various sizes of skeletons (approximately 1-2 microm) and through-pores (approximately 2-8 microm) in a fused-silica capillary (50-200 microm I.D.). The columns were evaluated in HPLC after derivatization to C18 phase. It was possible to prepare monolithic silica structures in capillaries of up to 200 microm I.D. from a mixture of tetramethoxysilane and methyltrimethoxysilane. As expected, a monolithic silica column with smaller domain size showed higher column efficiency and higher pressure drop. High external porosity (> 80%) and large through-pores resulted in high permeability (K = 8 x 10(-14) -1.3 x 10(-12) m2) that was 2-30 times higher than that of a column packed with 5-mirom silica particles. The monolithic silica columns prepared in capillaries produced a plate height of about 8-12 microm with an 80% aqueous acetonitrile mobile phase at a linear velocity of 1 mm/s. Separation impedance, E, was found to be as low as 100 under optimum conditions, a value about an order of magnitude lower than reported for conventional columns packed with 5-microm particles. Although a column with smaller domain size generally resulted in higher separation impedance and the lower total performance, the monolithic silica columns showed performance beyond the limit of conventional particle-packed columns under pressure-driven conditions.     

A comparative spectroscopic investigation of21Ne and21F by pickup reactions

The reactions²²Ne(d, t)²¹Ne and²²Ne(d, τ)²¹F have been investigated in a parallel experiment atE _d=52MeV. Energy spectra of tritons andτ particles have been measured up to excitation energies of 18MeV in both²¹Ne and²¹F nuclei. Thel values could be determined, and spectroscopic factors have been obtained by a DWBA analysis of the measured angular distributions. Together with the results from a preceding \({}^{22}Ne(\vec d, \tau ){}^{21}F\) experiment, several spins could be determined in²¹F. From a comparison of the triton andτ particle spectra,T=3/2 states in²¹Ne could be identified and on this basis the new information on spins of²¹F states could be transferred to their analog states in²¹Ne. The completeT _< andT _> parts of the (2s, 1d) strengths could be observed. The 1p strength is highly fragmented. Of theT _< part only 60% of the 1p1/2 and 40% of the lp3/2 strength could be found, but the totalT _> part of the 1p strength could be localized. The spectroscopic results for positive parity states are in qualitatively good agreement with shell model predictions.     

A new synthesis, including asymmetric synthesis, of spiro[4.n]alkenones from three components: cyclic ketones, chloromethyl p-tolyl sulfoxide, and acetonitrile; and a formal total synthesis of racemic acorone

1-Chlorovinyl p-tolyl sulfoxides were synthesized from several kinds of cyclic ketones and chloromethyl p-tolyl sulfoxide in good yields. Treatment of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium at −78°C to room temperature gave spirocyclic enaminonitriles in high yields. Acidic treatment of the enaminonitriles afforded spiro[4.n]alkenones in good yields. By using an unsymmetrical cyclic ketone, α-tetralone, and optically active chloromethyl p-tolyl sulfoxide, this procedure afforded enantiomerically pure spiro[4.5]decenone in good yield with excellent asymmetric induction from the sulfoxide chiral center. By using this method a formal total synthesis of a racemic spirocyclic sesquiterpene, acorone, was realized.