Inelastic light scattering at the second critical micellar formation of lecithin

Quasielastic light scattering provides a direct probe of the diffusional mobility of large particles in solution. Analysis of the light scattering spectra of natural lecithin as a function of scattering angle and concentration in hydrophilic and lipophilic solvents supports the conclusion that the second critical micelle transition is associated with the elongation of spherical molecular aggregates into cylindrical or ellipsoidal particles. The effective radius of the scattering entity below the second critical point is significantly less in nonpolar solvents. The latter result is explained in terms of amphiphilic lipid-solvent interactions.     

Nickel-catalyzed arylation of acrolein diethyl acetal: a substitute to the 1,4-addition of arylhalides to acrolein

[reaction: see text] In the presence of catalytic amount of NiBr(2) as catalyst precursor, organic halides are reductively coupled at 70 degrees C with acrolein diethyl acetal to give (Z)- and (E)-enolethers by allylic deplacement of an alkoxy group. Subsequent hydrolysis affords beta-arylated aldehydes.     

The vibrationless A<--X transition of the jet-cooled deuterated methyl peroxy radical CD3O2 by cavity ringdown spectroscopy

The nearly rotationally resolved spectrum of the A (2)A(')<--X (2)A(") 0(0)(0) transition of perdeutero methyl peroxy near 1.35 microm has been studied via pulsed cavity ringdown spectroscopy. Albeit, this is a weak transition, it is possible to observe the spectrum under jet-cooled conditions (approximately 15 K) by combining a source of narrow-bandwidth radiation (approximately 250 MHz) with a supersonic slit-jet expansion incorporating an electric discharge. The near infrared radiation was obtained by using stimulated Raman scattering and a pulsed, nearly Fourier-transform-limited Ti:sapphire amplifier seeded by a scanable cw Ti:sapphire ring laser. The experimental spectrum has been fitted using a model Hamiltonian that includes the rigid body rotation of an asymmetric top and the spin-rotation interaction. An excellent quality fit was obtained resulting in the determination of 15 molecular parameters characterizing the A and X states. Other results reported for CD(3)O(2) include an estimate of the radical concentration and the vibronic transition dipole from the observed absorption intensities. Details about the spectral linewidths are also discussed.     

Strain control in germanium nanowires: the use of a silicon nitride shell

The core–shell geometry is a strong tool for inducing and controlling strains in nano‐objects in order to tune their optoelectronic properties. We synthesized and characterized core–shell nanostructures by depositing a non‐epitaxial silicon nitride shell around germanium nanowires. Scanning electron microscopy as well as energy dispersive X‐ray spectroscopy confirms the structural integrity of the heterostructures, and grazing incidence X‐ray diffraction measurements reveal the presence of a radial tensile strain in the Ge nanowires. A control of this strain is then demonstrated up to 0.3% by adjusting the SiN_x shell thickness versus Ge nanowire diameter. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Sequencing Lys-N Proteolytic Peptides by ESI and MALDI Tandem Mass Spectrometry

In this study, we explored the MS/MS behavior of various synthetic peptides that possess a lysine residue at the N-terminal position. These peptides were designed to mimic peptides produced upon proteolysis by the Lys-N enzyme, a metalloendopeptidase issued from a Japanese fungus Grifola frondosa that was recently investigated in proteomic studies as an alternative to trypsin digestion, as a specific cleavage at the amide X-Lys chain is obtained that provides N-terminal lysine peptide fragments. In contrast to tryptic peptides exhibiting a lysine or arginine residue solely at the C-terminal position, and are thus devoid of such basic amino acids within the sequence, these Lys-N proteolytic peptides can contain the highly basic arginine residue anywhere within the peptide chain. The fragmentation patterns of such sequences with the ESI-QqTOF and MALDI-TOF/TOF mass spectrometers commonly used in proteomic bottom-up experiments were investigated.     

A multiparameter optimization in middle-down analysis of monoclonal antibodies by LC–MS/MS

In antibody-based drug research, a complete characterization of antibody proteoforms covering both the amino acid sequence and all posttranslational modifications remains a major concern. The usual mass spectrometry-based approach to achieve this goal is bottom-up proteomics, which relies on the digestion of antibodies but does not allow the diversity of proteoforms to be assessed. Middle-down and top-down approaches have recently emerged as attractive alternatives but are not yet mastered and thus used in routine by many analytical chemistry laboratories. The work described here aims at providing guidelines to achieve the best sequence coverage for the fragmentation of intact light and heavy chains generated from a simple reduction of intact antibodies using Orbitrap mass spectrometry. Three parameters were found crucial to this aim: the use of an electron-based activation technique, the multiplex selection of precursor ions of different charge states, and the combination of replicates.