Progress in the accuracy enhancement for elemental analysis by quadrupole-based plasma-SNMS

The elemental quantification in plasma-based SNMS is hampered by the matrix dependence of the detection efficiencies. The signals of elements of unknown compounds can only be converted to concentrations with mean detection factors resulting in concentrations with an uncertainty mainly given by the matrix effect. This situation can be considerably improved by energy measurements of the sputtered particles. The energy distribution (ED) can be used in two ways. First, the exact knowledge of the ED to each detected element allows an element specific integration of the directly sputtered atoms eliminating thermal species from resputtered wall deposition. For a set of copper compounds the spread of the Cu detection factors could be reduced from ± 63% for the conventional measurement to ± 35% using energy resolved data. Second, the shape of the ED of postionised atoms differs considerably from all interfering species, such as clusters as well as twice charged atoms which could superimpose on the atomic signals. A quantitative shape analysis of the measured ED was developed to correct for these interfering species. Examples are given for both superpositions with cluster intensities and interferences with twice charged intensities. To reduce the additional time necessary to obtain the ED, the number of energy resolved data points was reduced in steps down to 3 points only which still reduced a superposition error to half of the value without ED based correction.     

Regioselectivite de la reaction des dialkyl cuprates de magnesium sur des aldehydes α,β-ethyleniques

Various magnesium organocuprates give conjugative addition products with α,β-ethylenic aldehydes, and even with acrolein. The enolates may be trapped with bromine or trimethylsilyl chloride.     

Pulse radiolysis and fourier transform infrared study of neopentyl peroxy radicals in the gas phase at 297 K

The ultraviolet absorption spectrum of the neopentyl peroxy radical (CH₃)₃CCH₂O₂, and the kinetics and products of its self reaction have been studied in the gas phase at 298 K. Absorption cross sections were quantified over the wavelength range 230–290 nm. The measured cross section at 250 nm was; Errors represent statistical (2σ) together with our estimate of potential systematic errors(15%). The kinetics of the decay of the UV absorption following the generation of the neopentyl peroxy radicals was complicated by the rapid decomposition of the (CH₃)₃CCH₂O radicals formed in channel (4a). By measuring the yield of t-butyl peroxy radicals, the branching ratio k_4a/(k_4a + k_4b) was determined to be 0.39 ± 0.03. The rate constant for the self reaction of neopentyl peroxy radicals was k₄ = (1.07 ± 0.22) × 10^?12 cm³ molecule^?1 s^?1. Quoted errors represent 2σ. These results are discussed with respect to the available literature data. © John Wiley & Sons, Inc.     

On the size consistence of a few approximate multireference CI schemes

Using the canonical problem of N separate electron pairs, theN dependence of approximate multireference CI schemes is analyzed. When the DCI is taken as multireference space, the second order Quasi Degenerate Many Body Perturbation Theory (QD(MB)PT) gives twice the expected correction, while the CIPSI algorithm gives 66% of it, and the MRDCI a vanishing part of it. A modified QDPT effective hamiltonian, and a combination of CIPSI and QDPT algorithms seem to give better trends.     

Zusammenh?nge zwischen Koordination und polarographischem Verhalten unterschiedlicher Alizarin S-Chelate

Zusammenfassung Alizarin S und seine 11-Metallchelate lassen sich an der Quecksilbertropfelektrode reduzieren. Aus der Beeinflussung der diffusionskontrollierten und der Adsorptionsstufe durch die Chelatbildung lassen sich Aussagen über die Konstitution und Ladung der adsorbierten Chelate machen: Beryllium wird in peri-, Aluminium und Gallium werden in ortho-Stellung des Alizarinmoleküls gebunden. Die 11-Chelate des Be und Al sind ungeladen. Das Ga-Chelat ist negativ geladen und enthält offensichtlich zusätzliche anionische Liganden.Wir danken der Deutschen Forschungsgemeinschaft, Bonn-Bad Godesberg, dem Minister für Wissenschaft und Forschung des Landes Nordrhein-Westfalen, Landesamt für Forschung, sowie dem Verband der Chemischen Industrie, Fonds der Chemie, für Sachbeihilfen.     

CHEMILUMINESCENCE AND ENERGY TRANSFER FROM SINGLET OXYGEN PAIRS

Abstract— Chemiluminescence and photochemiluminescence of systems generating excited (singlet) molecular oxygen has been studied at low temperature in fluid media. A possible interpretation is proposed: that dimers of singlet oxygen are directly or indirectly responsible for the observed emission, the species [¹δg +¹σg⁺] predominating. Energy transfer to a fluorescent molecule is possible only when conditions of spectral overlap, required for transfer by inductive resonance, are fulfilled. Evidence is also presented for the formation of a transient complex between oxygen and a sensitiser or acceptor molecule [S…O₂], which is the precursor of singlet oxygen in these systems. However, other possible mechanisms cannot be excluded.     

A theoretical study of the formation of the parent phosphinine C5H5P from the flash vacuum thermolysis of diallylvinylphosphine

The gas-phase decomposition of diallylvinylphosphine 1 into C5H5P 12 is studied by DFT/6-311+G(d,p) calculations with the B3LYP functional, followed by single-point energy-only calculations at the CCSD(T)/6-311+G(d,p) level. According to these calculations, the first step involves a retro-ene elimination that yields 3-phosphahexatrienes 2Z and 2E. Both compounds equilibrate through the formation of 1,2- and 3,4-dihydrophosphetes 3 and 4, and it is shown that the formation of 2Z is favored by the exothermic formation of the 3,4-dihydrophosphinine 5 through a 6pi-electrocyclization. Though 5 can easily isomerize into 2,3- (6) and 1,2-diyhydrophosphinines (7) by successive 1,5-hydrogen shifts, the formation of 12 from 5, 6, or 7 through an elimination of H2 is found to be a high energy process. It is also shown that the elimination of H2 from lambda5-phosphinine 8 following a C2v pathway is a symmetry-forbidden process. Finally, 1,4-dihydrophosphinine 9, which can be formed through a 1,4-hydrogen shift from lambda5-phosphinine 8, is found to be a convenient precursor of 12 through a 1,4-elimination of H2. The formation of 9 from 5 involves the intermediary formation of 3-phosphabicyclo[3.1.0]hex-2-ene 10. The mechanism eventually proposed for the formation of 12 from 2Z is given in Scheme 16 at the CCSD(T) level.     

The Binary System BaF2/AlF3

The system BaF₂/AlF₃ is investigated by X-ray and D.T.A., and the liquid-solid phase diagram is established. Five ternary fluorides are disclosed: trimorphic BaAlF₅, Ba₃Al₂F₁₂, Ba₅AlF₁₉, polymorphic Ba₃AlF₉ and Ba₅AlF₁₃. Neutron thermodiffractometry experiments are performed to specify some parts of the diagram. The cell parameters of the fluorides are given and the results are discussed and compared with those of the previous works.     

Approaching exponential growth with a self-replicating peptide

Self-replicating peptide systems hold great promise for a wide range of technological applications, as well as to address fundamental questions pertaining to the molecular origins of life. The development of self-replicating compounds capable of high efficiency, however, has remained elusive. Here we disclose a successful strategy whereby modulation of coiled-coil stability results in remarkable catalytic efficiency for self-replication. By shortening the peptide to the minimum length necessary for coiled-coil formation a highly efficient self-replicating system was obtained due to very low background reaction rates, bringing the efficiency close to naturally occurring enzymes.     

Une nouvelle methoxylation d'hydroperoxy-3 indolines issues de la photo-oxygenation d'indoles en milieu reducteur

3-Hydroperoxy-1,3,6-trimethyl-2-phenyl indolines coming from the sensitized photooxygenation of the indoles in presence of KBH₄ rearrange partially in basic methanol into the corresponding 3-hydroxy-6-methoxymethyL indolines.