Thermal decomposition of surface compounds for the generation of small quantities of acetaldehyde: Calibration of a thermal desorption-gas chromatography-flame ionization detection

The paper presents a new method for the generation of acetaldehyde in the amounts that allow to calibrate the measuring system. The method is based on thermal decomposition of surface compounds at the range 130-190 °C, in which an acetaldehyde as the decomposition product is released. The synthetic pathway leading to the desired surface compounds is described. Investigations demonstrated that the synthesis of the compounds on the surface of the support material (silica gel) was carried out homogeneously. The technique proposed was used for the generation of gaseous standard mixtures containing acetaldehyde for the calibration of a thermal desorber-gas chromatograph-flame ionization detector system.     

Analysis of organotin compounds by grignard derivatization and gas chromatography-ion trap tandem mass spectrometry

The determination of organotin compounds in water using gas chromatography-tandem mass spectrometry (GC-MS-MS) is described. Several organotin derivatives were synthesized by the reaction of organotin chlorides with Grignard reagents such as methyl-, propyl- and pentylmagnesium halides. After the optimization of the GC-MS-MS conditions, several derivatizations with the Grignard reagents were compared by evaluating the molar responses and volatilities of the derivatives and derivatization yields. As a result, the derivatizing reagent of choice is pentylmagnesium bromide. Calibration curves for the mono-, di- and tributyltins and mono-, di- and triphenyltins with pentylmagnesium bromide were linear in the range of 0.5-100 pg of Sn. The instrumental detection limits of six organotins ranged from 0.20 to 0.35 pg of Sn. The recovery tests from water samples (500 ml) were performed by using sodium diethyldithiocarbamate (DDTC) as a complexing reagent. Except for monophenyltin, the absolute recoveries of organotins from pure water at 200 ng of Sn/l were satisfactory. The recoveries calibrated by surrogate compounds (perdeuterated organotin chlorides) ranged from 71 to 109%. The method detection limits ranged from 0.26 to 0.84 pg of Sn (500-ml sample). This method was applied to the recovery of organotins from river water and seawater. The calibrated recoveries were between 90 and 122%.     

Racemic ofloxacin separation by supported-liquid membrane extraction with two organic phases

As the relation of chirality and activities of drugs is researched deeply, people become to re-alize the clinic importance of chirality. The different enantiomers of a drug can have vastly differ-ent pharmacological activities, pharmacokinetic processes and toxicity[1,2]. The most well-docu- mented example is that of the drug substance thalidomide. Bitter lessons and scientific research promote the interest in single-enantiomer drugs, so the potential of the chiral drug market is enormous[3]. …     

Evaluation of the efficiency of extraction of PAHs from diesel particulate matter with pressurized solvents

Pressurized Fluid Extraction (PFE) was evaluated for the extraction of polycyclic aromatic hydrocarbons (PAHs) and nitro-derivatives from diesel particulate matter. Extraction conditions were set up by performing several tests in which temperature, solvent strength, pressure, and static time were gradually increased. The results obtained on a laboratory test material made of a "lean" (low content of soluble fraction) Diesel particulate matter indicate that very severe conditions were needed in order to obtain better recoveries of the higher molecular weight molecules. Moreover, extraction efficiency seems to be influenced by the amount of soluble matter in the particulate, so that a "lean" particulate appears more difficult to extract. Recoveries of the deuterated standards of certain PAHs (i.e. indeno[1,2,3- cd]pyrene) were incomplete even with the toughest conditions tested. Experiments carried out on a certified material (SRM 1650 from NIST) also indicate that PFE can perform a better extraction of some of the PAHs than the method used for certification, but still incomplete. Comparison of results obtained on the SRM with different extraction techniques suggests that the composition of the extract varies considerably with the extraction technique and conditions. It is relevant to notice that recent Diesel engines produce leaner particulate: for future materials more drastic extraction conditions will be required.     

A Highly Sensitive and Selective Assay for Cysteine Using the Chemiluminescence Reaction of Luminol and Hydrogen Peroxide

A very simple, highly sensitive and selective chemiluminescence (CL) method was established for the determination of cysteine. This method is based on the fact that the CL reaction of luminol and hydrogen peroxide can be greatly enhanced by cysteine. The CL intensities at maximum light emission were linearly correlated with the concentration of cysteine over the range of 2.0×10^–8–6.0×10^–6molL^–1 with a detection limit of 7.5×10^–9molL^–1. The relative standard deviation was 1.7% for the determination of 1.0×10^–7molL^–1 cysteine (n=9). The feasibility of utilizing the proposed method for the determination of total concentration of cysteine in human serum was examined.     

Reduction of (imine)Pt(IV) to (imine)Pt(II) complexes with carbonyl-stabilized phosphorus ylides

A novel method is reported for generation of the difficult-to-obtain (imine)Pt(II) compounds that involves reduction of the corresponding readily available Pt(IV)-based imines by carbonyl-stabilized phosphorus ylides, Ph3P=CHCO2R, in nonaqueous media. The reaction between neutral (imino)Pt(IV) compounds [PtCl4[NH=C(Me)ON=CR1R2]2] [R1R2 = Me2, (CH2)4, (CH2)5, (Me)C(Me)=NOH], [PtCl4[NH=C(Me)ONR2]2] (R = Me, Et, CH2Ph), (R1 = H; R2 = Ph or C6H4Me; R3 = Me) as well as anionic-type platinum(IV) complexes (Ph3PCH2Ph)[PtCl5[NH=C(Me)ON=CR2]] [R2 = Me2, (CH2)4, (CH2)5] and 1 equiv of Ph3P=CHCO2R (R = Me, Et) proceeds under mild conditions (ca. 4 h, room temperature) to give selectively the platinum(II) products (in good to excellent isolated yields) without further reduction of the platinum center. All thus prepared compounds (excluding previously described Delta4-1,2,4-oxadiazoline complexes) were characterized by elemental analyses, FAB mass spectrometry, IR and 1H, 13C[1H], 31P[1H] and 195Pt NMR spectroscopies, and X-ray single-crystal diffractometry, the latter for [PtCl2[NH=C(Me)ON=CMe2]2] [crystal system tetragonal, space group P4(2)/n (No. 86), a = b = 10.5050(10) A, c = 15.916(3) A] and (Ph3PCH2CO2Me)[PtCl3(NCMe)] [crystal system orthorhombic, space group Pna2(1) (No. 33), a = 19.661(7) A, b = 12.486(4) A, c = 10.149(3) A]. The reaction is also extended to a variety of other Pt(II)/Pt(IV) couples, and the ylides Ph3P=CHCO2R are introduced as mild and selective reducing agents of wide applicability for the conversion of Pt(IV) to Pt(II) species in nonaqueous media, a route that is especially useful in the case of compounds that cannot be prepared directly from Pt(II) precursors, and for the generation of systematic series of Pt(II)/Pt(IV) complexes for biological studies.     

Liquid chromatographic isolation of coplanar PCB congeners on an activated carbon stationary phase

A rapid and uncomplicated method for the fractionation of PCBs leading to an isolation of the highly toxic non-ortho substituted PCBs is described. The liquid chromatographic separation was achieved on a stationary phase consisting of activated carbon and Celite 545. Using eluents with different polarity, isolation of the non-ortho substituted PCBs in a single fraction was achieved. The fractions were analysed by GC/MS. The method was tested by the determination of non-ortho substituted PCBs in technical mixtures (Aroclor 1254 and Aroclor 1242). The results were compared with those obtained by using an HPLC fractionation on a porous graphitic carbon column. Finally, the micro-column fractionation was used for the determination of non-ortho substituted PCBs in native soil samples. Received: 5 March 1997 / Revised: 4 June 1997 / Accepted: 6 June 1997     

Copper-assisted oxidation of catechols into quinone derivatives

Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases.

An antioxidant catechol transforms following intramolecular redox reactions into highly reactive oxygen species, a semiquinone and a quinone, on copper.     

Planar defects in β-alumina

Sodium β-alumina crystals were elaborated by melting of a mixture of Na₂CO₃ and Al₂O₃ or by PbO flux evaporation and were studied by transmission electron microscopy. They exhibit regular planar defects lying in the {11.0} prismatic planes. These defects are described as antiphase boundaries for the cationic sublattice with fault vectors $\text{1}\text{2}\text{〈10.0〉}$ (such faults do not affect the anionic sublattice). As a consequence it would be interesting to study precisely the structure of the sodium β cationic lattice in the vicinity of the melting point.