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.     

The effect of the source pressure on the abundance of ions of noncovalent protein assemblies in an electrospray ionization orthogonal time-of-flight instrument

The effect of elevating the pressure in the interface region of an electrospray ionization orthogonal time-of-flight mass spectrometer on the ion intensity of different noncovalent protein assemblies has been investigated. Elevating the pressure in the interface region generally led to an enhanced detection of high m/z ions. The optimum pressure was found to be dependent on the m/z value of the ions. This pressure effect should be carefully addressed when relating ion abundance in the mass spectra to solution phase abundance of noncovalent protein assemblies.     

Aminosulf(ox)ides as ligands for Iridium(I)-catalyzed asymmetric transfer hydrogenation

A new class of efficient catalysts was developed for the asymmetric transfer hydrogenation of unsymmetrical ketones. A series of chiral N,S-chelates (6-22) was synthesized to serve as ligands in the iridium(I)-catalyzed reduction of ketones. Both formic acid and 2-propanol proved to be suitable as hydrogen donors. Sulfoxidation of an (R)-cysteine-based aminosulfide provided a diastereomeric ligand family containing a chiral sulfur atom. The two chiral centers of these ligands showed a clear effect of chiral cooperativity. In addition, aminosulfides containing two asymmetric carbon atoms in the backbone were synthesized. Both the sulfoxide-containing beta-amino alcohols and the aminosulfides derived from 1,2-disubstituted amino alcohols gave rise to high reaction rates and moderate to excellent enantioselectivities in the reduction of various ketones. The enantioselective outcome of the reaction was favorably affected by selecting the most appropriate hydrogen donor. Enantioselectivities of up to 97% were reached in the reduction of aryl-alkyl ketones.     

Observation of cavity-mediated long-range light forces between strongly coupled atoms

We report on the observation of long-range forces between ultracold rubidium atoms that are mutually coupled by the field of a driven high-finesse optical cavity. Even for much less than one photon in the cavity on average, the forces strongly influence the spatial distribution of the atoms. This manifests itself as an asymmetric normal-mode spectrum of the strongly coupled atoms-cavity system. Expressions are given for the dipole force and the diffusion coefficient for the atoms in the presence of the other atoms. The data agree well with calculated spectra, which include the full motional dynamics of the many-atom system.     

Trapping and observing single atoms in a blue-detuned intracavity dipole trap

A single atom strongly coupled to a cavity mode is stored by three-dimensional confinement in blue-detuned cavity modes of different longitudinal and transverse order. The vanishing light intensity at the trap center reduces the light shift of all atomic energy levels. This is exploited to detect a single atom by means of a dispersive measurement with 95% confidence in 10 micros, limited by the photon-detection efficiency. As the atom switches resonant cavity transmission into cavity reflection, the atom can be detected while scattering about one photon.     

Feedback cooling of a single neutral atom

We demonstrate feedback cooling of the motion of a single rubidium atom trapped in a high-finesse optical resonator to a temperature of about 160 μK. Time-dependent transmission and intensity-correlation measurements prove the reduction of the atomic position uncertainty. The feedback increases the 1/e storage time into the 1 s regime, 30 times longer than without feedback. Feedback cooling therefore rivals state-of-the-art laser cooling, but with the advantages that it requires less optical access and exhibits less optical pumping.     

A Robust, Environmentally Benign Catalyst for Highly Selective Hydroformylation

By a sol-gel process a rhodium complex containing a diphosphane with a large natural P-Rh-P bite angle is covalently anchored in a silica matrix (see picture). The immobilized catalyst is a very selective hydroformylation catalyst that is completely and conveniently separated from the product and can be reused in numerous cycles.     

Protein expression dynamics during replicative senescence of endothelial cells studied by 2-D difference in-gel electrophoresis

Endothelial senescence contributes to endothelium dysfunctionality and is thereby linked to vascular aging. A dynamic proteomic study on human umbilical vein endothelial cells, isolated from three umbilical cords, was performed. The cells were cultured towards replicative senescence and whole cell lysates were subjected to 2-D difference gel electrophoresis (DIGE). Despite the biological variability of the three independent isolations, a set of proteins was found that showed senescence-dependent expression patterns in all isolations. We focused on those proteins that showed significant changes, with a paired analysis of variance (RM-ANOVA) p-value of < or =0.05. Thirty-five proteins were identified with LC-Fourier transform MS, and functional annotation revealed that endothelial replicative senescence is accompanied by increased cellular stress, protein biosynthesis and reduction in DNA repair and maintenance. Nuclear integrity becomes affected and cytoskeletal structure is also changed. Such important changes in the cell infrastructure might accelerate endothelium dysfunctionality. This study provides biological information that will initiate studies to further unravel endothelial senescence and gain more knowledge about the consequences of this process in the in vivo situation.     

Macromolecular assembly of Helicobacter pylori urease investigated by mass spectrometry

The supramolecular assembly of Helicobacter pylori urease was studied by nanoflow electrospray ionization orthogonal time-of-flight mass spectrometry. The measured molecular mass of the urease complex of 1.06 MDa corresponds to a dodecameric (alphabeta)(12) assembly of urease alpha (26 kDa) and beta (61 kDa) subunits. The dodecamer disassembles readily into (alphabeta)(3) subunits in solution and under controlled collisional-induced dissociation in the gas phase. This is in strong support of an ((alphabeta)(3))(4) architecture consistent with the recently published x-ray structure. In vitro, the alpha and beta subunits are capable of re-assembling to (alphabeta)(3), but not further to the dodecameric complex.