Application of ion-exchange cartridge clean-up in food analysis IV. Confirmatory assay of benzylpenicillin, phenoxymethylpenicillin, oxacillin, cloxacillin, nafcillin and dicloxacillin, in bovine tissues by liquid chromatography-electrospray ionization tandem mass spectrometry

A multiresidue analytical method was developed for the confirmation of benzylpenicillin (PCG), phenoxymethylpenicillin (PCV), oxacillin (MPIPC), cloxacillin (MCIPC), nafcillin (NFPC) and dicloxacillin (MDIPC) in bovine tissues using electrospray ionization liquid chromatography-tandem mass spectrometry (LC-ESI-MS-MS) with a product ion scan mode. All penicillins gave [M-H]-, [M-H-CO2]- and [M-H-141]- as the product ion, when [M-H]- was selected as the precursor ion. Combination of an ion-exchange cartridge clean-up and the LC-ESI-MS-MS method can reliably identify all of these penicillins fortified at a concentration of 0.05 mg/kg in bovine tissues, including liver, kidney and muscle. The limits of confirmation satisfy the maximum residue limits for each of the penicillins established by the World Health Organization, US Food and Drug Administration, European Union and Japan.     

Reactivity of the indole ring in palladium(II) complexes of 2N1O-donor ligands: cyclopalladation and pi-cation radical formation

The Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethylindole (Htbu-iepp), 1-methyl-3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethylindole (Htbu-miepp), 3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]methylindole (Htbu-impp), and 3-(N-2-pyridylmethyl-N-4-hydroxybenzylamino)ethylindole (Hp-iepp) (H denotes a dissociable proton), were synthesized, and the structures of [Pd(tbu-iepp)Cl] (1a), [Pd(tbu-iepp-c)Cl] (1b), [Pd(tbu-miepp)Cl] (3), and [Pd(p-iepp-c)Cl] (4) (tbu-iepp-c and p-iepp-c denote tbu-iepp and p-iepp bound to Pd(II) through a carbon atom, respectively) were determined by X-ray analysis. Complexes 1a prepared in CH(2)Cl(2)/CH(3)CN and 3 prepared in CH(3)CN have a pyridine nitrogen, an amine nitrogen, a phenolate oxygen, and a chloride ion in the coordination plane. Complex 1b prepared in CH(3)CN has the same composition as 1a and was revealed to have the C2 atom of the indole ring bound to Pd(II) with the Pd(II)-C2 distance of 1.973(2) A. The same Pd(II)-indole C2 bonding was revealed for 4. Interconversion between 1a and 1b was observed for their solutions, the equilibrium being dependent on the solvent used. Reaction of 1b and 4 with 1 equiv of Ce(IV) in DMF gave the corresponding one-electron-oxidized species, which exhibited an ESR signal at g = 2.004 and an absorption peak at approximately 550 nm, indicating the formation of the Pd(II)-indole pi-cation radical species. The half-life, t(1/2), of the indole radical species at room temperature was calculated to be 20 s (k(obs) = 3.5 x 10(-)(2) s(-)(1)) for 1b. The cyclic voltammogram for 1b in DMF gave two irreversible oxidation peaks at E(pa) = 0.68 and 0.80 V (vs Ag/AgCl), which were ascribed to the oxidation processes of the coordinated indole and phenolate moieties, respectively.     

Measurements of 127I M?ssbauer spectra for iodine compounds

127I M?ssbauer spectra of good quality were obtained at 20 K using a Zn127mTe source produced by high flux neutron irradiation of 66Zn-126Te at reactor core. The M?ssbauer spectra for KI and some iodine(III) compounds with absorption intensity of about 5% suggest that the 127I M?ssbauer spectroscopy is useful in elucidating the bonding nature of the iodine compounds. Preparative method of the M?ssbauer source and experimental technique are reported in detail.     

Production of submicron-sized multihollow polymer particles by alkali/cooling method

Submicron-sized styrene-methacrylic acid copolymer particles, which were produced by emulsion copolymerization, were changed to those having multihollow structure by treating stepwise the emulsion as follows. First alkali treatment was carried out at higher temperature than the glass transition temperature and subsequently the emulsion was cooled by keeping it at room temperature. This was named alkali/cooling method. The effects of methacrylic acid content, pH, time and temperature in the alkali treatment on the formation of multihollow structure were clarified.Part CLV of the series Studies on suspension and emulsion     

Synthesis of Ultrafine SiC Powders from Carbon-Silica Hybridized Precursors with Carbothermic Reduction

Inorganic-organic hybrid gels were prepared by simultaneous condensation of the liquid mixture of ethyl silicate, ethyl borate and water soluble phenol resin with low molecular weight. The liquid mixtures were changed into lightly colored transparent gels after a catalyst addition and stirring. The obtained gels were crushed, dried and fired in controlled conditions to yield the inorganic precursors. Since the tailored inorganic precursors mainly consisted of SiO2 and carbon, silicon carbide was formed with the heat treatments in an Ar atmosphere beyond 1773 K with carbothermic reduction. The properties and morphology of the formed silicon carbide powders in terms of the starting precursor compositions and the conditions of the carbothermic reduction were investigated with SEM, XRD and TG-DTA analysis.     

Synthesis and properties of bowl‐shaped homotriazacalix[3 and 6] arenes and the acyclic analogues

Bowl‐shaped chiral homotriazacalixarenes were prepared by the cyclization reactions of chiral triamines with three equimolar amounts of bis(chloromethyl) phenols or bis(chloromethyl) phenol‐formaldehyde dimers in moderate yields. The corresponding acyclic phenol‐formaldehyde oligomers were also synthesized. The structural analysis of the macrocycles by nmr and circular dichroism spectra imply the existence of chiral transmission from the point chirality of the cysteine bridge to the cyclophane moiety. Their cyclic and acyclic compounds have a π‐base cavity large enough to include the ammonium ion.     

Characterization and quantitation of clarithromycin polymorphs by powder X-ray diffractometry and solid-state NMR spectroscopy

Characterization of clarithromycin polymorph was performed by solid-state cross polarization and magic angle spinning (CP/MAS) 13C-NMR spectroscopy. Two polymorphs, form II and form I, of clarithromycins indicated characteristic resonances of C1 carbonyl carbon at 176.2 and 175.2 ppm, respectively. Since each peak of C1 carbon was well separated in the spectrum of the two polymorphs, we performed quantitative analysis of the polymorphic fraction from the peak area of these peaks. The peak area of form I was found to linearly increase with an increase of its content, with a correlation coefficient of above 0.99. Solid-state NMR was found to be a useful technique to determine the characteristics of the polymorphic forms.     

Palladium(0) complexes coordinated with substituted olefins and tertiary phosphine ligands

New palladium(0) complexes with a variety of coordinated olefins [Pd(olefin)(PMePh₂)₂] (II) (olefin = styrene, ethyl methacrylate, methyl methacrylate, methyl acrylate, methacrylonitrile, and dimethyl maleate), were prepared by the reactions of [PdEt₂(PMePh₂)₂] (I) with corresponding olefins in toluene. These complexes were characterized by means of elemental analysis, IR and ¹H NMR spectroscopy and the chemical reactions. The dissociation of the coordinated olefin from complex II in solution was confirmed by spectroscopic studies of [Pd(mma)(PMePh₂)₂] (mma = methyl methacrylate). From the variable temperature NMR study, kinetic parameters for the dissociation process were determined as E_a = 7 kcal/mol, and ΔS³ (293 K) = -30 cal/deg · mol. Some new hydrido complexes, [Pd(H)ClL₂] (IV) (L = PMePh₂, PEtPh₂ and PEt₂Ph), were prepared by the reactions of [Pd(olefin)L₂] with dry HCl.     

Synthesis and properties of new polyesters having tetrahydrofuran rings in their main chains

New polyesters 6a–6c consisting of 2,4-linked tetrahydrofuran rings were synthesized by bulk polycondensation of methyl trans- and cis-4-hydroxytetrahydrofuran-2-carboxylates ( 5a and 5b ) and a stereoisomeric mixture of methyl 4-hydroxy-5-methyltetrahydrofuran-2-carboxylate ( 5c ) at high temperature. These monomers were prepared from methyl glycolate or methyl lactate and diethyl maleate through a four-step reaction sequence. The polycondensation was carried out without solvent at different temperatures ranging from 150 to 220°C. Titanium isopropoxide was most effective among the catalysts examined, giving polyesters with number-average molecular weights up to 2 × 10⁴. Polyester 6a consisting of trans-2,4-linked tetrahydrofuran rings was soluble in trifluoroacetic acid and a mixed solvent of chloroform and methanol (10/1, v/v). Polyester 6b composed of cis-2,4-linked tetrahydrofuran rings was soluble in dimethyl sulfoxide and dimethylformamide in addition to the two solvents for 6a . Polyester 6c with 5-methyl-substituted tetrahydrofuran rings was composed of a mixture of stereoisomeric units and thus was soluble in a variety of solvents including chloroform, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, and dimethylformamide. The glass transition temperatures of 6a, 6b , and 6c determined by DSC were 109, 88, and 66°C. These polyesters were found to be very slowly hydrolyzed in a neutral phosphate buffer solution at ambient temperature. © 1993 John Wiley & Sons, Inc.