A novel access to tetrahydro-beta-carbolines via one-pot hydroformylation/fischer indole synthesis: rearrangement of 3,3-spiroindoleninium cations

The two component one-pot hydroformylation/Fischer indole synthesis sequence of 2,5 dihydropyrroles and phenyl hydrazines allows a facile and convenient access to tetrahydro-beta-carbolines in moderate to good yields.     

Influence of chain length and degree of branching of alcohol + chlorobenzene mixtures on determination and modelling of V by CEOS and CEOS/G mixing rules

The densities of binary mixtures of (1-propanol, or 1-butanol, or 2-butanol, or 1-pentanol + chlorobenzene) have been measured at temperatures 288.15, 293.15, 298.15, 303.15, 308.15 and 313.15 K and atmospheric pressure while for the system (2-methyl-2-propanol + chlorobenzene) measurements were performed at the same pressure and temperatures 303.15, 308.15, 313.15, 318.15 and 323.15 K. All measurements were performed by means of an Anton Paar DMA 5000 digital vibrating-tube densimeter. Excess molar volumes V^E were determined and fitted by the Redlich–Kister equation. It was observed that in all cases, V^E increase with rising of temperature. The values of limiting excess partial molar volumes have been calculated, as well. The obtained results have been analysed in terms of specific molecular interactions present in these mixtures taking into consideration effect of the chain length of alcohols, degree of branching in the chain, relative position of the alkyl and OH group in an alcohol and the effect of temperature on them. In addition, the correlation of V^E binary data was performed with the Peng–Robinson–Stryjek–Vera cubic equation of state (PRSV CEOS) coupled with the van der Waals (vdW1) and CEOS/G^E mixing rule introduced by Twu, Coon, Bluck and Tilton (TCBT). Also, the possibility of cross prediction between V^E and VLE by means of the NRTL parameters of G^E model available in literature and those incorporated in the TCBT model was tested.     

TG-DTA-FTIR analysis and isoconversional reaction profiles for thermal and thermo-oxidative degradation processes in black chokeberry (<Emphasis Type="Italic">Aroniamelanocarpa</Emphasis>)

The thermal and thermo-oxidative processes in Aroniamelanocarpa (black chokeberry) were investigated using combined thermo-analytical (TG-DTA) and spectroscopic (FTIR) experimental techniques. Isoconversional analysis revealed that the process in an inert (argon) atmosphere was probably governed by chlorogenic acid degradation, where autocatalysis (described by the empirical ?esták-Berggren model) might occur due to water already present in the early stages of the process through hydrolysis. Thermal degradation is described by the intrinsic kinetic parameters, where the degradation rate increases proportionally with an increase in the heating rate. Under oxidative conditions, the process was found to be primarily driven by neochlorogenic acid degradation. The thermo-oxidative degradation of Aroniamelanocarpa fresh samples can be described by two competitive reactions, where it was established that a cyanidin-3-glucosylrutinoside degradation made a significant contribution to a comprehensive kinetics. This study showed the targeting of the neochlorogenic acid in Aroniamelanocarpa fresh samples to have a strong hydrogen-donating activity, thereby rendering it capable of very efficiently entrapping the peroxy radicals. Current research has demonstrated that the relative contribution of the two competitive reactions to the overall process is highly dependent on the heating rate of the system under consideration.     

C*-Convex Sets and Completely Positive Maps

We prove a geometric version of an operator valued Hahn–Banach theorem and use it to study sets K that are A-convex over a unital C*-algebra A in the sense that \({\sum_{j=1}^{n} a_{j}^{*}y_{j}a_{j}\in K}\) whenever \({y_{j}\in K}\) and \({a_{j}\in A}\) with \({\sum_{j=1}^{n}a_{j}^{*}a_{j}=1}\). We show how weak* compact such sets can be realized as concrete sets of unital completely positive maps. An application to C*-extreme points is also presented.     

A dynamic study of earthworm feeding ecology -using stable isotopes

Changes in the specific diet of earthworms with time in relation to landuse changes and two different climates were studied by analysing (13)C and (15)N natural abundance in soils and animals. Soil samples from three depths (0-10, 10-20 and 20-30 cm) and earthworms were collected from two sites: Santiago (Northwest Spain) and North Wyke (Southwest England) both consisting of replicated long-term grasslands and recently converted to maize plots. Earthworms were hand-sorted in the field at the peak of the maize growth and after harvesting at both sites. In the Spanish plots, nine and eight earthworm species, all belonging to the three ecological categories (epigeic, anecic and endogeic), were found under maize and permanent pasture, whereas at the English site five and seven different species were, respectively, identified. At both sites (13)C isotopic values of the earthworm tissues reflected changes in diet from C(3) to C(4) with epigeic and epi/anecic worms in the maize plots showing one delta unit difference in relation to the ones found in the grassland plots. Anecic worms seemed to be less responsive to landuse changes. The higher (13)C values of the Spanish soils were also reflected in the earthworm tissues when compared with the English samples. (15)N values showed no clear relationship with the cropping treatments but were clearly related to the ecological grouping, with endogeic worms reaching the highest values whereas for the epigeic and epi/anecic species the lowest values were obtained. This finding was also previously recorded by other authors1 and suggests that, in the future, stable isotope techniques could also be a useful tool in taxonomic studies. Copyright 1999 John Wiley & Sons, Ltd.     

Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

Multiple ionization of argon in coincidence with projectile ions in 60–120 MeV Si q+-Ar collisions

A projectile ion-recoil ion coincidence technique has been employed to study the multiple ionization and the charge transfer processes in collisions of 60–120 MeV Si ^q+ (q = 4−14) ions with neutral argon atoms. The relative contribution of different ionization channels, namely; direct ionization, electron capture and electron loss leading to the production of slow moving multiply charged argon recoil ions have been investigated. The data reported on the present collision system result from a direct measurement in the considered impact energy for the first time. The total ionization cross-sections for the recoil ions are shown to scale as q ^1.7/E _p ^0.5 , where E _p is the energy in MeV of the projectile and q its charge state. The recoil fractions for the cases of total- and direct ionizations are found to decrease with increasing recoil charge state j. The total ionization fractions of the recoils are seen to depend on q and to show the presence of a ‘shell-effect’ of the target. Further, the fractions are found to vary as 1/j ² upto j = 8+. The average recoil charge state 〈j〉 increases slowly with q and with the number of lost or captured electrons from or into the projectile respectively. The projectile charge changing cross-sections σ _qq′ are found to decrease with increasing q for loss ionization and to increase with q for direct-and capture ionization processes respectively. The physics behind various scaling rules that are found to follow our data for different ionization processes is reviewed and discussed.     

Measuring derived acoustic power of an ultrasound surgical device in the linear and nonlinear operating modes

Objective and motivationThe method for measuring derived acoustic power of an ultrasound point source in the form of a sonotrode tip has been considered in the free acoustic field, according to the IEC 61847 standard. The main objective of this work is measuring averaged pressure magnitude spatial distribution of an sonotrode tip in the free acoustic field conditions at different electrical excitation levels and calculation of the derived acoustic power at excitation frequency (f₀ ≈ 25 kHz). Finding the derived acoustic power of an ultrasonic surgical device in the strong cavitation regime of working, even in the considered laboratory conditions (anechoic pool), will enable better understanding of the biological effects on the tissue produced during operation with the considered device.Experimental methodThe pressure magnitude spatial distribution is measured using B&;K 8103 hydrophone connected with a B&;K 2626 conditioning amplifier, digital storage oscilloscope LeCroy Waverunner 474, where pressure waveforms in the field points are recorded. Using MATLAB with DSP processing toolbox, averaged power spectrum density of recorded pressure signals in different field positions is calculated. The measured pressure magnitude spatial distributions are fitted with the appropriate theoretical models.Theoretical approachesIn the linear operating mode, using the acoustic reciprocity principle, the sonotrode tip is theoretically described as radially oscillating sphere (ROS) and transversely oscillating sphere (TOS) in the vicinity of pressure release boundary. The measured pressure magnitude spatial distribution is fitted with theoretical curves, describing the pressure field of the considered theoretical models. The velocity and displacement magnitudes with derived acoustic power of equivalent theoretical sources are found, and the electroacoustic efficiency factor is calculated. When the transmitter is excited at higher electrical power levels, the displacement magnitude of sonotrode tip is increased, and nonlinear behaviour in loading medium appears, with strong cavitation activity produced hydrodynamically. The presence of harmonics, subharmonics and ultraharmonics as a consequence of stable cavitation is evident in the averaged power spectral density. The cavitation noise with continuous frequency components is present as a consequence of transient cavitation. The averaged pressure magnitude at the frequency components of interest (discrete and continous) in the field points is found by calculating average power spectral density of the recorded pressure waveform signal using the welch method. The frequency band of interest where average power spectral density is calculated is in the range from 15 Hz up to 120 kHz due to measurement system restrictions. The novelty in the approach is the application of the acoustic reciprocity principle on the nonlinear system (sonotrode tip and bubble cloud) to find neccessary acoustic power of the equivalent acoustic source to produce the measured pressure magnitude in the field points at the frequency components of interest.ResultsIn the nonlinear operating mode, the ROS model for the considered sonotrode tip is chosen due to the better agreement between measurement results and theoretical considerations. At higher excitation levels, it is shown that the averaged pressure magnitude spatial distribution of discrete frequency components, produced due to stable cavitation, can be fitted in the far field with the inverse distance law. The reduced electroacoustic efficiency factor, calculated at excitation frequency component as ratio of derived acoustic power with applied electrical power, is reduced from 40% in the linear to 3% in the strong nonlinear operating mode. The derived acoustic power at other frequency components (subharmonic, harmonic and ultraharmonic) is negligible in comparison with the derived acoustic power at excitation frequency.Discussion and conclusionsThe sonotrode tip and loading medium are shown in the strong cavitation regime as the coupled nonlinear dynamical system radiating acoustic power at frequency components appearing in the spectrum. The bubble cloud in the strong nonlinear operating mode decreases the derived acoustic power significantly at the excitation frequency.