New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Intercalation of Benzamide into Kaolinite

Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press.     

Molecular dynamics reveal that isoDGR-containing cyclopeptides are true αvβ3 antagonists unable to promote integrin allostery and activation

Ain't got that swing(-out): The cyclopeptide isoDGR is emerging as a new αvβ3 integrin binding motif. Agreement between the results of computational and biochemical studies reveals that isoDGR-containing cyclopeptides are true αvβ3 integrin antagonists that block αvβ3 in its inactive conformation (see scheme). isoDGR-based ligands may give αvβ3 antagonists without paradoxical effects.     

Iron-related toxicity effects of single-walled carbon nanotubes in human placental cells (BeWo) investigated by X-ray fluorescence microscopy

As the prospect of human beings exposed to new nanomaterials increases, there are growing concerns about the foetal exposure and effects of such nanomaterials during pregnancy. Among others, due to their ample usage, it becomes urgent to address the vulnerability of the human placental barrier to carbon nanotubes (CNTs). Recently, by applying a combination of advanced synchrotron-based X-ray microscopy and X-ray fluorescence (XRF) techniques, we demonstrated that raw single-walled CNTs (SWCNTs) may cause an asbestos-like iron-related toxicity in mesothelial (MeT5A) cells. This work shows the results obtained with the same approach and experimental conditions in human choriocarcinoma (BeWo) cells as a placental model. XRF microscopy in mild and soft X-ray regimes was used to map the distribution of P, S, Ca, and Fe in exposed and control cells, whereas absorption and phase-contrast imaging (soft X-ray microscopy) provided simultaneous morphological information. The findings show that exposure to SWCNTs affects cell viability and causes a small increase in intracellular iron content, further confirmed by the stimulation of the ferritin protein. It is interesting to note that the iron changes are negligible when highly purified SWCNTs are used. In all tested conditions, including exposure to iron sulfate, the iron accumulation or ferritin increase was much lower in BeWo cells than in MeT5A ones, suggesting a different iron metabolism and possibly a lower vulnerability of the placental barrier to iron-rich nanomaterials.     

Computation of the inverse Laplace transform based on a collocation method which uses only real values

We develop a numerical algorithm for inverting a Laplace transform (LT), based on Laguerre polynomial series expansion of the inverse function under the assumption that the LT is known on the real axis only. The method belongs to the class of Collocation methods (C-methods), and is applicable when the LT function is regular at infinity. Difficulties associated with these problems are due to their intrinsic ill-posedness. The main contribution of this paper is to provide computable estimates of truncation, discretization, conditioning and roundoff errors introduced by numerical computations. Moreover, we introduce the pseudoaccuracy which will be used by the numerical algorithm in order to provide uniform scaled accuracy of the computed approximation for any x   with respect to e^σx${\mathrm{e}}^{\sigma x}$. These estimates are then employed to dynamically truncate the series expansion. In other words, the number of the terms of the series acts like the regularization parameter which provides the trade-off between errors.     

Detection of the singularities of a complex function by numerical approximations of its Laurent coefficients

For several applications, it is important to know the location of the singularities of a complex function: just for example, the rightmost singularity of a Laplace Transform is related to the exponential order of its inverse function. We discuss a numerical method to approximate, within an input accuracy tolerance, a finite sequence of Laurent coefficients of a function by means of the Discrete Fourier Transform (DFT) of its samples along an input circle. The circle may also enclose some singularities, since the method works with the Laurent expansion. The DFT is computed by the FFT algorithm so that, from a computational point of view, the efficiency is guaranteed. The function samples may be obtained by solving a numerical problem such as, for example, a differential problem. We derive, as consequences of the method, some new outcomes able to detect those singularities which are close to the circle and to discover if the singularities are all external or internal to the circle so that the Laurent expansion reduces to its regular or singular part, respectively. Other singularities may be located by means of a repeated application of the method, as well as an analytic continuation. Some examples and results, obtained by a first implementation, are reported.