Intramolecular C-H insertion using NHC-di-rhodium(II) complexes: the influence of axial coordination

In this work we show that the intramolecular C-H insertion of diazo-acetamides catalysed by di-rhodium(II) complexes can be highly influenced by the axial ligand on the di-rhodium(II) complex. Axially monocoordinated NHC-Rh₂(OAc)₄ complexes have a distinct reactivity from the parent Rh₂(OAc)₄ complex affording the cyclisation products in different rates and selectivities. Surprisingly, a new reaction mode emerged when using these complexes which led to a decarbonylation pathway.     

Multiple response optimization: a global criterion‐based method

Processes and products have by nature many quality characteristics that must be in some sense optimized simultaneously. With this aim, a method which can be used easily and efficiently by practitioners for optimizing multi‐response problems is proposed. Implementation steps and considerations, in addition to optimization measures to assess method's solutions and guide the analyst in finding an effective compromise solution, are also presented. Three classical examples from the literature are used to assess the performance of several prominent methods in the response surface methodology (RSM) framework and help practitioners make a better‐informed choice among them. Copyright © 2010 John Wiley & Sons, Ltd.     

Hydrophobic interaction membrane chromatography for plasmid DNA purification: Design and optimization

Chromatography is one of the key operations in the downstream processing of plasmid DNA (pDNA). However, the increased demand for highly purified pDNA experienced in recent years has made clear the need for alternative processes capable of retaining the advantages of conventional chromatography, such as selectivity, while providing increased throughput at a lower cost. The work presented in this article outlines the development and optimization of an alternative hydrophobic interaction membrane chromatography process for the purification of pDNA. The studies included the modification of functionalized membrane supports with a linear alkyl chain ligand and the testing of chromatographic performance of these membranes. Three modification procedures were tested and the membranes were screened for their capacity and selectivity. The modified membranes could separate the model plasmid pVAX1‐LacZ (6050 bp) from impurities in clarified Escherichia coli cell lysates (specifically RNA), with good resolution. Subsequent optimization of elution profiles with the best‐performing modified membrane, resulted in a high purification factor of 4.7, competitive with its bead process counterpart, and a plasmid yield of 73%.     

Characterization of the volatile fraction emitted by Pinus spp. by one- and two-dimensional chromatographic techniques with mass spectrometric detection

The chemical composition of the needles of P. pinea, P. pinaster, P. halepensis, P. nigra, P. brutia, P. patula, P. radiata, P. taeda, P. elliotti, P. kesiya, P. sylvestris and P. eldarica was investigated. Headspace solid-phase microextraction and steam distillation extraction were used to collect the volatile fractions. Samples were analyzed using one-dimensional gas chromatography (1D-GC) and comprehensive two-dimensional gas chromatography (GC × GC) associated with a quadrupole and a time-of-flight mass detectors. Results showed that the analytical capabilities of 1D-GC are partially limited by the separation power of the columns. The higher sensibility and the absence of peak skewing of the time-of-flight mass analyzer, with the use of automated peak finding and deconvolution algorithms, allowed for the detection of trace components with qualitative full spectra and the extraction of true mass spectra from coeluting compounds, promoting their reliable identification and thus significantly improving results obtained by 1D-GC/MS, when using a quadrupole mass analyzer. The use of GC × GC resulted in enhanced separation efficiency and increased signal to noise ratio (sensitivity) of the analytes, maximizing mass spectra quality and improving compound detection and identification. This work shows the use of 1D-GC/ToFMS for the analysis of pine needles volatiles, achieving the detection of 177 compounds, that is more than twice the number previously identified by standard 1D-GC/MS. The analysis by GC × GC for the same sample allowed the detection of 212 compounds. The enantioselective GC × GC analysis performed for all the Pinus spp. under study achieved the detection of 422 different compounds. Cross-over phenomena according to operational conditions are highlighted and discussed.     

Evolution of first-order sidebands from multiple FWM processes in HiBi optical fibers

The generation of two idler waves inside a high birefringent (HiBi) optical fiber through three four-wave mixing (FWM) processes is studied theoretically. The coupled-equations for the field amplitudes are derived and analytically solved, in the co-polarized and orthogonal polarization schemes. The obtained solutions take into account the delayed Raman response of the medium. The polarization sensitivity of the generation of the idler waves is analyzed. Results show that the stimulated Raman scattering does not change the efficiency of the idler wave generation in the co-polarized scheme, whereas in the orthogonal polarization scheme that nonlinear process decreases the efficiency of the four-wave mixing processes. Results also show that this set of multiple four-wave mixing processes is physically quite different from the typical single or dual pump four-wave mixing configurations. Findings show that the power transfer from the pumps to the idler fields can lead to a monotonous growth, or a periodic evolution of the sidebands along the fiber. Results show that the process efficiency varies greatly with the angle between the two pump polarizations.     

Transport through graphene on SrTiO3

We report transport measurements through graphene on SrTiO(3) substrates as a function of magnetic field B, carrier density n, and temperature T. The large dielectric constant of SrTiO(3) very effectively screens long-range electron-electron interactions and potential fluctuations, making Dirac electrons in graphene virtually noninteracting. The absence of interactions results in an unexpected behavior of the longitudinal resistance in the N=0 Landau level and in a large suppression of the transport gap in nanoribbons. The "bulk" transport properties of graphene at B=0 T, on the contrary, are completely unaffected by the substrate dielectric constant.     

Spatial distribution of AT- and GC-rich DNA within interphase cell nuclei of Triatoma infestans Klug

Heterochromatin bodies in single- and multichromocentered interphase cell nuclei of Triatoma infestans, a vector of Chagas disease, have been suggested to contain AT-rich DNA, based on their positive response to Q-banding and Hoechst 33248 treatment. No information exists on whether GC-rich DNA is also present in these nuclei and whether it plays a role on chromatin condensation. Considering that methodologies more precise than those previously used to determine DNA base composition in situ are currently available, and that the spatial distribution of chromatin areas differing in composition in interphase cell nuclei of different species is a matter of interest, the localization of AT- and GC-rich DNA in T. infestans nuclei is revisited here. The methodologies used included DAPI/AMD and CMA(3)/Distamycin differential staining, Feulgen-DNA image analysis following Msp I and Hpa II enzymatic digestion, 5-methylcytidine immunodetection, AgNOR response, confocal microscopy, and the 5-aza-2'-deoxycytidine (5-AZA) demethylation assay. The results identified the presence of AT-rich/GC-poor DNA in chromocenters and evenly distributed AT and GC sequences in euchromatin. A GC-rich DNA zone encircling the chromocenters was also found but it could not be associated with NOR regions. To corroborate the DNA AT-richness in T. infestans nuclei, bioinformatic analyses were also performed. Methylated cytosine was evident at some points of the chromocenters' edge in single- and multichromocentered nuclei and at the euchromatin of multichromocentered nuclei and could be transiently affected by the 5-AZA treatment. The present results suggest that in the particular case of chromocenters of the hemipteran T. infestans, cytosine methylation is not a relevant factor involved in chromatin condensation.     

Vortices and Jacobian varieties

We investigate the geometry of the moduli space of N$N$ vortices on line bundles over a closed Riemann surface Σ$\Sigma$ of genus g>1$g>1$, in the little explored situation where 1≤N<g$1\le N<g$. In the regime where the area of the surface is just large enough to accommodate N$N$ vortices (which we call the dissolving limit), we describe the relation between the geometry of the moduli space and the complex geometry of the Jacobian variety of Σ$\Sigma$. For N=1$N=1$, we show that the metric on the moduli space converges to a natural Bergman metric on Σ$\Sigma$. When N>1$N>1$, the vortex metric typically degenerates as the dissolving limit is approached, the degeneration occurring precisely on the critical locus of the Abel–Jacobi map of Σ$\Sigma$ at degree N$N$. We describe consequences of this phenomenon from the point of view of multivortex dynamics.