Rovibrational photoionization dynamics of methyl and its isotopomers studied by high-resolution photoionization and photoelectron spectroscopy

High-resolution photoionization and pulsed-field-ionization zero-kinetic-energy photoelectron spectra of CH(3), CH(2)D, CHD(2), and CD(3) have been recorded in the vicinity of the first adiabatic ionization threshold following single-photon excitation from the ground neutral state using a narrow-bandwidth vacuum-ultraviolet laser. The radicals were produced from the precursor molecules methyl-bromide, methyl-iodide, dimethyl-thioether, acetone, and nitromethane by 193 nm excimer photolysis in a quartz capillary and were subsequently cooled to a rotational temperature T(rot) approximately equal to 30 K in a supersonic expansion. Nitromethane was identified as a particularly suitable photolytic precursor of methyl for studies by photoionization and threshold photoelectron spectroscopy. Thanks to the cold rotational temperature reached in the supersonic expansion, the rotational structure of the threshold ionization spectra could be resolved, and the photoionization dynamics investigated. Rydberg series converging on excited rotational levels of CH(3) (+) could be observed in the range of principal quantum number n=30-50, and both rotational autoionization and predissociation were identified as decay processes in the threshold region. The observed photoionization transitions can be understood in the realm of an orbital model for direct ionization but the intensity distributions can only be fully accounted for if the rotational channel interactions mediated by the quadrupole of the cation are considered. Improved values of the adiabatic ionization thresholds were derived for all isotopomers [CH(3): 79 356.2(15) cm(-1), CH(2)D: 79 338.8(15) cm(-1), CHD(2): 79 319.1(15) cm(-1), and CD(3): 79 296.4(15) cm(-1)].     

A novel application of sample entropy to the electrocardiogram of atrial fibrillation

Nowadays, several non-linear regularity estimators have been successfully applied to invasive atrial electrograms in order to characterize the atrial electrical activity organization during atrial fibrillation (AF). This arrhythmia is the most common encountered in clinical practice, accounting for approximately one-third of all the hospitalizations for cardiac rhythm disturbances. However, from a clinical point of view, it would be more desired to evaluate atrial activity (AA) organization from surface electrocardiographic (ECG) recordings, since they can be obtained easily and cheaply and the risks associated with invasive recordings could be avoided. In this work, Sample Entropy (SampEn) is proposed to assess the organization degree of the AA obtained from surface ECGs. To this respect, a reliable and non-invasive organization estimator would allow the prediction of spontaneous AF termination, since invasive studies have shown more organized electrical activity signals during the preceding instants of AF termination. The proposed method computed SampEn over the AA obtained from TQ segments, free of QRST complexes, and was validated with a database containing a training set of 20 AF recordings, with known termination properties, and a test set of 30 recordings. A simulation study showed that patients with heart rates of 130 bpm and above must be handled with care, because TQ intervals could be considerably reduced (<50 ms). As an overall result, spontaneous AF termination in 90% of the learning and test recordings was correctly predicted through this novel approach. As a conclusion, this work introduces the application of a non-linear regularity index able to assess significative differences in AA organization from surface ECG recordings during AF.     

NMR: A good tool to ascertain σ-silane or σ-borane formulations?

NMR has played a major role in the characterization of dihydrogen complexes and a number of polyhydrides have been reformulated as dihydrogen complexes on the basis of NMR data. If dihydrogen complexes remain the most widely studied class of σ-complexes, silane compounds are also well recognized as an important family of σ-complexes and more recently a few σ-borane compounds have been isolated. One important problem is the discrimination between a σ-formulation and the corresponding hydrido(silyl) or hydrido(boryl) oxidative addition product. In this review we will discuss key literature data on silane and borane complexes to illustrate the benefit gained by using multinuclear NMR spectroscopy to better define the structures and bonding modes. Our goal is also to help the reader to appreciate the limits of the method and to provide valuable insights into the problem of secondary interactions.     

Novel N-aryl and N-heteroaryl sulfamide synthesis via palladium cross coupling

A novel and efficient synthesis of N-aryl and N-heteroaryl sulfamides via an intermolecular palladium-catalyzed coupling process has been developed. The reactions proceeded with good to excellent yields and were tolerant of a wide range of functional groups. [reaction: see text]     

Determination of total ribonucleotide pool in plant materials by high-pH anion-exchange high-performance liquid chromatography following extraction with potassium hydroxide

A new, improved method that only requires a potassium hydroxide extraction procedure is presented for the analysis of a full nucleotide pool in plant materials. Quantification was performed by high-pH anion-exchange chromatography (HPAEC) with UV detection after a potassium hydroxide extraction, and allowed the quantification of 13 linear ribonucleotides in a single run. The method has been validated by comparison of six extraction methods and also by measurement of the intracellular nucleotide levels of three plant species (cell cultures and leaves). The evolution of the nucleotide pool of Nicotiana tabacum cell culture during growth has also been measured, and showed an increase in the pool until the fifth day, where the growth rate reaches a maximum, after which a decrease was observed.     

Novel enantioselective synthesis of 1,3-butadien-2-ylmethanols via tandem alkylbromide-epoxide vinylations using dimethylsulfonium methylide

[reaction: see text] The treatment of chiral trans-disubstituted and trisubstituted 2,3-epoxy-1-bromides with an excess of dimethylsulfonium methylide 1 affords the corresponding 1,3-butadien-2-ylmethanols in good to excellent yields via a double one-carbon homologation.     

Acces aux [pyridyl-2′]-2 phosphorines

An optimized phosphole-phosphorin conversion procedure has been used for preparing the first known 2-(2′-pyridyl)phosphorin from 1-phenyl-3,4-dimethylphosphole and picolinic acid chloride.     

Exact solution of the asymmetric exclusion model with particles of arbitrary size

A generalization of the simple exclusion asymmetric model is introduced. In this model an arbitrary mixture of molecules with distinct sizes s=0,1,2, ..., in units of lattice space, diffuses asymmetrically on the lattice. A related surface growth model is also presented. Variations of the distribution of the molecules sizes may change the excluded volume almost continuously. We solve the model exactly through the Bethe ansatz and the dynamical critical exponent z is calculated from the finite-size corrections of the mass gap of the related quantum chain. Our results show that for an arbitrary distribution of molecules, the dynamical critical behavior is on the Kardar-Parizi-Zhang universality.     

Selective determination of cobalt in a strongly acidic medium by flow injection analysis

Summary A selective method for the FIA spectrophotometric determination of Co(II) based on the use of pyridoxal 4-phenylthiosemicarbazone as reagent was developed with the aid of a straightforward 4-line flow injection manifold. The physical variables involved in the process were optimized as follows: injected sample volume 260 l; reactor lengths 116 and 150 cm. The proposed method allows the determination of cobalt over the concentration range 0.4–14.4 g ml^–1 at a sampling rate of 48 samples h^–1. The method is subject to very few interferences thanks to the fact that the strongly acidic medium used prevents the formation of most of the complexes of the reagent with other ions. It was applied to the determination of cobalt in steels.