Stereoselective synthesis of unnatural α-amino acid derivatives through photoredox catalysis

A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural α-amino acids. The developed protocol allows the use of ubiquitous carboxylic acids as radical precursors without prior derivatization. The protocol utilizes near-stoichiometric amounts of the imine and the acid radical precursor in combination with a catalytic amount of an organic acridinium-based photocatalyst. Alternative mechanisms for the developed transformation are discussed and corroborated by experimental and computational studies.

A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural α-amino acids.     

Defect formation on surfaces bombarded by energetic multiply charged proteins: Implications for the conformation of gas-phase electrosprayed ions

Indirect information on the conformation of highly charged molecular ions may be obtained by monitoring their collisional cross sections and the course of simple gas-phase reactions such as hydrogen-deuterium exchange. In this work, another indirect but more visually oriented approach is explored: electrosprayed protein ions are accelerated toward a highly oriented pyrolytic graphite surface and the resulting single-ion defects are imaged by scanning force and tunneling microscopy. All protein impacts generated shallow hillocks: the shapes depended on the identity and charge state of the incident protein. Lysozyme and myoglobin, both compact, globular proteins in the native state, produced compact, almost circular hillocks. However, hillocks generated by myoglobin that had been denatured in the solution phase were elongated, and the elongation was positively correlated with the charge state of the ion. It appears that structural information about gas-phase multiply charged proteins can be derived from imprints generated by energetic protein impacts on surfaces.     

Electron capture dissociation of substance P using a commercially available Fourier transform ion cyclotron resonance mass spectrometer

Electron capture dissociation of the peptide Substance P is reported for the first time, with an unmodified, commercially available Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. The fragmentation pattern is compared with that obtained with collisionally induced dissociation of the ions in the electrospray ion source, and note that electron capture dissociation gives a more easily interpreted spectrum, showing mainly C-fragments. With the exception of the proline residues, which require cleavage of two chemical bonds, we observe all C-fragmental we find the bias voltage of the electron gun not to be very critical.     

Superporous agarose beads as a hydrophobic interaction chromatography support

Superporous agarose beads were used as a support for hydrophobic interaction chromatography. These beads have large connecting flow pores in addition to their normal diffusion pores. The flow pores, which are approximately one fifth of the overall diameter of the superporous agarose beads, were earlier shown to give the beads improved mass transfer properties relative to homogeneous agarose beads (Gustavsson and Larsson, J. Chromatogr. A, 734 (1996) 231–240). Superporous agarose beads and homogeneous agarose beads of the same particle size range (106–180 μm) were derivatized with phenyl groups. The properties of the superporous beads were then compared with the homogeneous beads in the separation of a mixture of three model proteins (ribonuclease A, lysozyme and bovine serum albumin) at various superficial flow velocities from 30 to 600 cm/h. The superporous beads gave satisfactory separation at flow velocities five times higher than was possible for homogeneous beads. The performance of the two types of beads was also compared in the purification of lactate dehydrogenase from a beef heart extract at a superficial flow velocity of 150 cm/h. The superporous beads performed considerably better, leading to twice the purification factor and twice the concentration of the desired product. The results were interpreted using the theoretical treatment given by Carta and Rodrigues (Carta and Rodrigues, Chem. Eng. Sci., 48 (1993) 3927).     

Comparison of preconditioned Krylov subspace iteration methods for PDE-constrained optimization problems

The governing dynamics of fluid flow is stated as a system of partial differential equations referred to as the Navier-Stokes system. In industrial and scientific applications, fluid flow control becomes an optimization problem where the governing partial differential equations of the fluid flow are stated as constraints. When discretized, the optimal control of the Navier-Stokes equations leads to large sparse saddle point systems in two levels. In this paper, we consider distributed optimal control for the Stokes system and test the particular case when the arising linear system can be compressed after eliminating the control function. In that case, a system arises in a form which enables the application of an efficient block matrix preconditioner that previously has been applied to solve complex-valued systems in real arithmetic. Under certain conditions, the condition number of the so preconditioned matrix is bounded by 2. The numerical and computational efficiency of the method in terms of number of iterations and execution time is favorably compared with other published methods.     

A Practical Procedure for the Solid-Phase Synthesis of Racemic 2,2′-Dihydroxy-1,1′-binaphthyl

Abstract: A high yielding solid-phase dimerisation of 2-naphthol by means of a ball-milling procedure is described.

     

An improved palladium(II)-catalyzed method for the synthesis of aryl ketones from aryl carboxylic acids and organonitriles

A palladium(II)-catalyzed decarboxylative protocol for the synthesis of aryl ketones has been developed. The addition of TFA was shown to improve the reaction yield and employing THF as solvent enabled the use of solid nitriles and in only a small excess. Using this method, five different benzoic acids reacted with a wide range of nitriles to produce 29 diverse (hetero)aryl ketone derivatives in up to 94% yield.     

Aromatic allylation via diazotization: metal-free C-C bond formation

A new method for the synthesis of allyl aromatic compounds not involving any metal-containing reagent or catalyst has been developed. Arylamines substituted with a large number of different substituents were converted via diazotizative deamination with tert-butyl nitrite in allyl bromide and acetonitrile to the corresponding allyl aromatic compounds. The allylation reaction was found to be suitable for larger scale synthesis due to short reaction times, a nonextractive workup, and robustness toward moisture, air, and type of solvent.     

Hyperpolarization of 13C through order transfer from parahydrogen: a new contrast agent for MRI

The order within proton pairs in organic molecules, resulting from hydrogenation with parahydrogen, can be transferred in great part to nearby carbon 13 spins through adequate field manipulations. The molecules with hyperpolarized 13C thus obtained can be used as new contrast agents of high efficiency in MRI. After a brief presentation of the hydrogenation process and apparatus, in relatively low magnetic field, we describe the procedure of order transfer to the 13C spins through a sudden drop from the initial field to zero field followed by an adiabatic remagnetization. The expected final polarizations in the absence of relaxation are given for several compounds. Finally, we show an example of MR images observed in vivo on animals as an illustration of the contrast capacity of this new method.     

Study of 19Na at SPIRAL

The excitation function for the elastic-scattering reaction p( ¹⁸Ne, p) ¹⁸Ne was measured with the first radioactive beam from the SPIRAL facility at the GANIL laboratory and with a solid cryogenic hydrogen target. Several broad resonances have been observed, corresponding to new excited states in the unbound nucleus ¹⁹Na. In addition, two-proton emission events have been identified and are discussed.