Iridium‐Catalyzed Arylative Cyclization of Alkynones by 1,4‐Iridium Migration

1,4‐Metal migrations enable the remote functionalization of C? H bonds, and have been utilized in a wide variety of valuable synthetic methods. The vast majority of existing examples involve the 1,4‐migration of palladium or rhodium. Herein, the stereoselective synthesis of complex polycycles by the iridium‐catalyzed arylative cyclization of alkynones with arylboronic acids is described. To our knowledge, these reactions involve the first reported examples of 1,4‐iridium migration.     

Bright soliton trains of trapped Bose-Einstein condensates

We variationally determine the dynamics of bright soliton trains composed of harmonically trapped Bose-Einstein condensates with attractive interatomic interactions. In particular, we obtain the interaction potential between two solitons. We also discuss the formation of soliton trains due to the quantum mechanical phase fluctuations of a one-dimensional condensate.     

Temperament Development Modeled as a Nonlinear Complex Adaptive System

Using approach-withdrawal (AW) as a specific instance of temperament, a theoretical model of temperament as a complex dynamic system is proposed. Developmental contextualism (Lerner, 1998) serves as a guiding theory in determining the structural components of the system and Kauffman's (1993) Boolean models of self-organization are adapted to estimate the parameter functions. In this model P(AW) = f(, ) where P(AW) is the probability density function of an approach or a withdrawal response, ( is a standardized parameter estimate of the biological sensitivity to stimulation, and is a standardized parameter estimate of the contextual response to an approach or withdrawal response. It is theorized that the functions of ( and follow a Hill function of the forms: d /dt = (²/c² + ²) – K₁ d /dt = ( ²/c² + ²) – K₂, where K₁, K₂, and c are system constants. This results in a double sigmoid function in which at extreme values of and the system stabilizes on a steady state of either approach or withdrawal response patterns. At intermediate parameter values the probability density functions of approach and withdrawal responses are wider. Thus, AW can be modeled as representing two basins of attraction. In addition, considerations are given to the systems sensitivity to initial conditions.     

Diffusion-weighted MRI: influence of intravoxel fat signal and breast density on breast tumor conspicuity and apparent diffusion coefficient measurements

Promising recent investigations have shown that breast malignancies exhibit restricted diffusion on diffusion-weighted imaging (DWI) and may be distinguished from normal tissue and benign lesions in the breast based on differences in apparent diffusion coefficient (ADC) values. In this study, we assessed the influence of intravoxel fat signal on breast diffusion measures by comparing ADC values obtained using a diffusion-weighted single shot fast spin-echo sequence with and without fat suppression. The influence of breast density on ADC measures was also evaluated. ADC values were calculated for both tumor and normal fibroglandular tissue in a group of 21 women with diagnosed breast cancer. There were systematic underestimations of ADC for both tumor and normal breast tissue due to intravoxel contribution from fat signal on non–fat-suppressed DWI. This ADC underestimation was more pronounced for normal tissue values (mean difference=40%) than for tumors (mean difference=27%, P<.001) and was worse in women with low breast tissue density vs. those with extremely dense breasts (P<.05 for both tumor and normal tissue). Tumor conspicuity measured by contrast-to-noise ratio was significantly higher on ADC maps created with fat suppression and was not significantly associated with breast density. In summary, robust fat suppression is important for accurate breast ADC measures and optimal lesion conspicuity on DWI.     

Synthesis of β-pyrrolic-modified porphyrins and their incorporation into DNA

A synthetic methodology for the synthesis of various β-pyrrolic-functionalised porphyrins and their covalent attachment to 2'-deoxyuridine and DNA is described. Palladium(0)-catalysed Sonogashira and copper(I)-catalysed Huisgen 1,3-dipolar cycloaddition reactions were used to insert porphyrins into the structure of 2'-deoxyuridine and DNA. Insertion of a porphyrin into the middle of single-stranded CT oligonucleotides possessing a 5'-terminal run of four cytosines was shown to trigger the formation of pH- and temperature-dependent i-motif structures. Porphyrin insertion also led to the aggregation of single-stranded purine-pyrimidine sequences, which could be dissociated by heating at 90 °C for 5 min. Parallel triplexes and anti-parallel duplexes were formed in the presence of the appropriate complementary strand(s). Depending on the modification, porphyrins were placed in the major and minor grooves of duplexes and were used as bulged intercalating insertions in duplexes and triplexes. In general, the thermal stabilisation of parallel triplexes possessing porphyrin-modified triplex-forming oligonucleotide (TFO) strands was observed, whereas anti-parallel duplexes were destabilised. These results are compared and discussed on the basis of the results of molecular modelling calculations.     

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Ohne Zusammenfassung     

Thermomechanical analysis of a toughened thermosetting system

The experimental results of viscoelastic mechanical tests, at five different levels of conversion, are reported for a thermoset composite matrix system toughened with an appropriate percentage of a thermoplastic polymer. The results from static tests are used to construct the master curves at a specific degree of cure, while the shift factors are compared with the corresponding values from dynamic experiments in order to assess the validity of the time-temperature superposition for each conversion. Neat resin plates were cured accurately, according to the full kinetics model for a dynamic and isothermal temperature regime; the conversion gradient in the plane and across the thickness of the plates was assessed by a thermal analysis of samples taken from different locations before extracting the samples from them. The viscoelastic behaviour of the resin matrix showed a sensible difference in the relaxation time spectrum upon conversion according to the provisional trend of mobility theory; a higher conversion induced a horizontal shift of the principal relaxation time for each level of conversion, which could be related very well to the glass transition at the same conversion. Good results were also obtained for the ultimate modulus of the resin at a temperature just before the onset of the co-curing phase for partially cured samples. Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 44, No. 2, pp. 265–278, March–April, 2008.     

Bond exciton model of alkenes and diene polymers

The bond exciton model, developed originally for alkane molecules, is applied here to a range of alkene molecules and diene polymers. The necessary empirical parameters are derived by comparison of the theory with the vacuum-ultraviolet absorption spectra of ethylene and a number of alkyl-substituted ethylenes, and these values are used to predict the energies, intensities and polarizations of the lower energy allowed valence transitions of fine diene polymers. Despite its simplicity the bond exciton model is found to give results in quite reasonable agreement with the available experimental data, and suggests that considerable excitation energy transfer may occur along the main chains of certain diene polymers.     

Finite element simulation of water circulation in the North Sea

The modelling of tidal effects, storm surges and currents in large bodies of water is considered. The solution is attempted using the evolutionary shallow water equations with velocities and wave heights as unknowns. Two finite element simulation models are described based on six noded triangular elements. Special consideration has been given to the adequacy of the models which were applied to the North Sea only after extensive tests in channels. Results for velocities and wave heights are compared and discussed. A set of conclusions on the applicability and scope of the models is presented.