Effects of aldehyde or dipyrromethane substituents on the reaction course leading to meso-substituted porphyrins

To better understand the effects of diverse substituents on reactions leading to porphyrins, pyrrole+aldehyde condensations and related reactions of dipyrromethanes were examined. The course of pyrrole+aldehyde condensations was investigated by monitoring the yield of porphyrin (by UV-Vis spectroscopy), reaction of aldehyde (by TLC), and changes in the composition of oligomers (by laser desorption mass spectrometry). Reaction reversibility was examined via exchange experiments. Reversibility of reactions leading to porphyrin was further probed with studies of dipyrromethanes. The reaction course was found to depend on the nature of the substituent and the acid catalyst. Alkyl or electron-donating substituents displayed levels of reversibility (exchange/scrambling) on par or greater than that of the phenyl substituent, whereas electron-withdrawing or sterically bulky substituents exhibited little to no reversibility. The results obtained provide insight into the electronic and steric effects of different substituents and should facilitate the design of synthetic plans for preparing porphyrinic macrocycles.     

Highly strained InxGa(1−x)As−InyAl(1−y)As (x>0.8,y<0.3) layers for short wavelength QWIP and QCL structures grown by MBE

Highly strained quantum cascade laser (QCL) and quantum well infrared photodetector (QWIPs) structures based on In_xGa_(1−x)As−In_yAl_(1−y)As (x>0.8,y<0.3) layers have been grown by molecular beam epitaxy. Conditions of exact stoichiometric growth were used at a temperature of 420°C to produce structures that are suitable for both emission and detection in the 2–5 μm mid-infrared regime. High structural integrity, as assessed by double crystal X-ray diffraction, room temperature photoluminescence and electrical characteristics were observed. Strong room temperature intersubband absorption in highly tensile strained and strain-compensated In_0.84Ga_0.16As/AlAs/In_0.52Al_0.48As double barrier quantum wells grown on InP substrates is demonstrated. Γ–Γ intersubband transitions have been observed across a wide range of the mid-infrared spectrum (2–7 μm) in three structures of differing In_0.84Ga_0.16As well width (30, 45, and 80 Å). We demonstrate short-wavelength IR, intersubband operation in both detection and emission for application in QC and QWIP structures. By pushing the InGaAs–InAlAs system to its ultimate limit, we have obtained the highest band offsets that are theoretically possible in this system both for the Γ–Γ bands and the Γ–X bands, thereby opening up the way for both high power and high efficiency coupled with short-wavelength operation at room temperature. The versatility of this material system and technique in covering a wide range of the infrared spectrum is thus demonstrated.     

On-line cysteine modification for protein analysis: new probes for electrochemical tagging nanospray mass spectrometry

A series of electrogenerated selective electrophiles based on substituted benzoquinones has been characterized as tags for l-cysteine and cysteine residues in proteins. The electrophiles are generated electrochemically from the corresponding hydroquinones. It is shown from mass spectrometry analysis that the electrogenerated benzoquinone can tag the biomolecules. The rate constants pertaining to the addition of l-cysteine onto the electrogenerated benzoquinones have been determined using electrochemical techniques. The substitution patterns have been unraveled leading to the assessment of site-specific rate constants. It is shown that the rate constants are primarily dependent on the electronic nature of the substituents as expressed by the Hammett substitution constant. The apparent tagging yields observed for l-cysteine in nanospray mass spectrometry experiments do not correspond to the yields expected from the electrochemical study, as the ionisation efficiencies are highly dependent on the tag. Finally, the on-line tagging has been tested using β-lactoglobulin A and myoglobin. Based on these results, it is concluded that the tagging reaction is selective towards cysteine when it takes place in the nanospray interface. The results show that the methodology presented can be used for a rapid characterization and identification of reactive sites in biomolecules.     

Kinetic study of the crosslinking reaction of 1,2‐polybutadiene with dicumyl peroxide in the absence and presence of vinyl acetate

The crosslinking reaction of 1,2-polybutadiene (1,2-PB) with dicumyl peroxide (DCPO) in dioxane was kinetically studied by means of Fourier transform near-infrared spectroscopy (FTNIR). The crosslinking reaction was followed in situ by the monitoring of the disappearance of the pendant vinyl group of 1,2-PB with FTNIR. The initial disappearance rate (R₀) of the vinyl group was expressed by R₀ = k[DCPO]^0.8[vinyl group]^−0.2 (120 °C). The overall activation energy of the reaction was estimated to be 38.3 kcal/mol. The unusual rate equation was explained in terms of the polymerization of the pendant vinyl group as an allyl monomer involving degradative chain transfer to the monomer. The reaction mixture involved electron spin resonance (ESR)-observable polymer radicals, of which the concentration rapidly increased with time owing to a progress of crosslinking after an induction period of 200 min. The crosslinking reaction of 1,2-PB with DCPO was also examined in the presence of vinyl acetate (VAc), which was regarded as a copolymerization of the vinyl group with VAc. The vinyl group of 1,2-PB was found to show a reactivity much higher than 1-octene and 3-methyl-1-hexene as model compounds in the copolymerization with VAc. This unexpectedly high reactivity of the vinyl group suggested that an intramolecular polymerization process proceeds between the pendant vinyl groups located on the same polymer chain, possibly leading to the formation of block-like polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4437–4447, 2004     

Analysis of semiconducting materials by high-resolution radiofrequency glow discharge mass spectrometry

The analytical capabilities of a high-resolution mass spectrometer in combination with a 13.56 MHz glow discharge ion source for the analysis of semiconducting materials (silicon carbide and gallium arsenide) were studied. It was shown that single positively charged ions of sample material have about 10 eV higher average energy than the ions of the discharge and residual gas. Therefore effective energy separation of the ions of analyte from the ions of the discharge and residual gas was achieved by adjusting the ion transfer optics (breadth and position of energy slit), which improves the analytical capabilities of the developed method.Some analytical applications are presented to illustrate the performance of r.f. GDMS for the bulk analysis of semiconducting materials. The results of the trace element analysis of gallium arsenide and silicon carbide samples are compared with data of independent methods (LIMS, ICP-AES, SIMS).Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthdayOn leave from the Institute of Inorganic Chemistry, 630090 Novosibirsk, Russia     

Reaction of D2 with palladium fulleride C60Pd4.9

Fullerene deuteride was obtained by the reaction of deuterium with solid palladium fulleride C₆₀Pd_4.9 under fairly mild conditions. The compound was identified by FD-MS, UV-Vis and IR spectroscopies, and TLC.Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 483–484, February, 1996     

Quantification of trace elements in human serum fractions by liquid chromatography and inductively coupled plasma mass spectrometry

On‐line coupling of LC and ICP‐MS has been used for fractionation and detection of species of Cu, Fe, I, Se and Zn in human serum. It has been shown that anion exchange chromatography provided better separation capability (both intra‐ and inter‐element) than size‐exclusion chromatography. The mobile phases for ion exchange chromatography consisted of Tris–HNO₃ buffer and ammonium salt (nitrate, acetate or formate). Formate was found to be the best mobile phase counter ion, enabling good chromatographic separation, and is acceptable for mass spectrometry too. The quantitative evaluation of element concentrations adhering to individual fractions was performed by the peak area normalization method. The repeatability of results ranged from 3 to 15% (depending on the element concentration level) and represented the main part of the result uncertainty. The accuracy of Cu and Zn fraction determinations was confirmed by comparison with the isotope dilution technique. Copyright © 2006 John Wiley & Sons, Ltd.     

Individual and center-of-mass resonances in the motional spectrum of an electron cloud in a Penning trap

We have examined experimentally the motional spectrum of an electron cloud confined in a Penning trap. When the axial oscillation is excited by a radio frequency field the resonance exhibits a double structure. Both components depend differently on the number of trapped electrons and have different shape and width. We conclude that one of them corresponds to the excitation of the individual electrons while the other is the center-of-mass mode of the cloud. The threshold behaviour of the center-of-mass resonance suggests that it is a parametric instability of a Mathieu type equation of motion. Received 11 July 2001 and Received in final form 12 November 2001     

Investigation of chemical decomposition of CCl4 on TiO2 near room temperature

Dissociative adsorption of CCl₄ on TiO₂ at 35 °C has been studied by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and electron spin resonance. CCl₄ decompose to form CO, CO₂, and CO₃ on the surface, at such a low temperature, in which CO₂ formation is not from CO oxidation on TiO₂, but CO₃ can be produced by CO and CO₂ adsorption. The Cl generated from CCl₄ decomposition is left on the surface and bonded to titanium ions. Mineralization of CCl₄ on TiO₂ involves the lattice oxygens. Thermodynamical driving force and possible reaction routes for CO and CO₂ formation in the CCl₄ decomposition on TiO₂ are discussed.