An improved procedure for the conversion of indolines into indoles

The addition of a sacrificial enamine (such as indole), or of a vinyl ether (like dihydropyran) to an indoline during dehydrogenation by phenylseleninic anhydride dramatically improves the yield of the corresponding indole. This is due to scavenging of Se¹¹ phenylselenenating species.     

Simultaneous off-shell excitation of He 23 S by an electron and one or more photons

We report data on the excitation of the 2³ S metastable state in helium by electrons in the presence of an intense laser field. The metastable signal is detected when the electron energy is insufficient to excite this state by itself. The additional energy comes from a pulsed CO₂ laser developing peak intensities in the interaction region in the 10⁸ W× cm^?2 range and requires the absorption of one or more photons. This process involves the active participation of all three bodies: the electron, the photon and the target atom. These data represent the first observation of this process when more than one photon is required.     

Perfluoro compounds as blood substitutes.

Inconceivable as it is, it has been proved that animals can survive after having had their blood massively or even totally replaced by emulsions of perfluorinated compounds in salines. “Bloodles” rats charged with an emulsion of perfluorotri-n-butylamine survived a five hour period in an atmosphere containing 50% oxygen and 50% carbon monoxide, i.e. in conditions where the transport of oxygen by the red cells is entirely blocked. This review discusses: (1) the experiments which have demonstrated the capability of blood substitutes based on perfluorinated compounds to sustain life; (2) the characteristics and preparation of the relevant perfluoro compounds and the production and handling of their emulsions; (3) their “physiology”, i.e. toxicity, life-span in the blood-stream, effect on the organs and their functions, and excretion properties. Obstacles remaining to be overcome in order to provide a safe blood substitute for medical practice include the availability of numerous series of well-defined pure and inert perfluorinated chemicals, the production of stable emulsions, the optimization of fluid balance, and the attainment of reasonable excretion rates. The accent is placed upon the role of the chemist in the progress of this research.     

Singlet exciplexes between a thioxanthone derivative and substituted aromatic quenchers: role of the resonance integral

Fluorescence quenching of a thioxanthone derivative by methyl- and methoxy-substituted benzenes (MeB and MeOB, respectively) is performed in solvents of different polarity. Emissive exciplexes are observed even in polar solvents and provide kinetic and spectroscopic data over a large scale of solvent polarity. These data were subsequently analyzed by use of a new theoretical model that leads to a thermodynamic relationship between exciplex and electron-transfer driving forces Delta G(exc) and Delta G(et), respectively. The remarkable agreement found between this model and both kinetic and spectroscopic data supports its validity. Moreover, the difference observed between MeB and MeOB compounds in quenching efficiency is analyzed by this model and provides the main parameters governing exciplex features, especially the resonance integral between locally excited and charge-transfer states.     

Parameter identification of thermophilic anaerobic degradation of valerate

The considered mathematical model of the decomposition of valerate presents three unknown kinetic parameters, two unknown stoichiometric coefficients, and three unknown initial concentrations for biomass. Applying a structural identifiability study, we concluded that it is necessary to perform simultaneous batch experiments with differenitial conditions for estimating these parameters. Four simultaneous batch experiments were conducted at 55°C, characterized by four different initial acetate concentrations. Product inhibition of valerate degradation by acetate was considered. Practical identification was done optimizing the sum of the multiple determination coefficients for all measured state viariables and for all experiments simultaneously. The estimated values of kinetic parameters and stoichiometric coefficients were characterized by the parameter correlation matrix, the confidence interval, and the student's t-test at 9% significance level with positive results except for the saturation constant, for which more eperiments for improving its identifiability should be conducted. In this article, we discussekinetic parameter estimation methods.     

Thermal denaturation of some proteins and its effect on their electrospray mass spectrat

The effects of beat on the electrospray mass spectra of eight globular proteins in solution were studied. These ranged from hardly noticeable to a dramatic shift in the mass spectrometric profile and a concomitant increase in ion abundance. This change is believed to be the result of thermal denaturation of the protein species in solution resulting in a transition from a more compact to a less compact conformation. We accounted for this transition by means of a recently proposed model based on aqueous solution acid/base equilibria. For cytochrome c, profiles calculated by means of this model agree well with experimental data. The ΔH of the denaturation reaction of cytochrome c in aqueous solution containing 0.2% acetic acid was calculated from experimental data to be 103.8 ± 9.2 kJ mol^?1, in good agreement with previous measurements.     

The μSR facilities at PSI

TheSR Facility Instruments presently available at PSI and the envisaged medium- and long-term developments are presented. The plans focus on further upgrades of the existing instruments and the development of new techniques using the very high fluxes becoming available at PSI, in particular the setup of a beamline with a fast kicker for muons on request (MORE) and the development of very low energy muon beams.