Influence of charge state and amino acid composition on hydrogen transfer in electron capture dissociation of peptides

Although conventional N-Cα bond cleavage in electron capture dissociation (ECD) of multiply-charged peptides generates a complementary c′ and z′ fragment pair, the N-Cα cleavage followed by hydrogen transfer from c′ to z′ fragments produces other fragments, namely c′ and z′. In this study, the influence of charge state and amino acid composition on hydrogen transfer in ECD is described using sets of peptides. Hydrogen transferred ionic species such as c′ and z′ were observed in ECD spectra of doubly-protonated peptides, while the triply-protonated form did not demonstrate hydrogen transfer. The extent of hydrogen transfer in ECD of doubly-protonated peptides was dependent on constituent amino acids. The ECD of doubly-protonated peptides possessing numerous basic sites showed extensive hydrogen transfer compared with ECD of less basic peptides. The extent of hydrogen transfer is discussed from the viewpoints of the structure of peptide ions, the possibility of internal hydrogen bonding and intermediate lifetime of complex [c′+z′].     

Giant out-of-plane spin component and the asymmetry of spin polarization in surface Rashba states of bismuth thin film

We have performed high-resolution spin- and angle-resolved photoemission spectroscopy of bismuth thin film on Si(111) to investigate the spin structure of surface states. Unlike the conventional Rashba splitting, the magnitude of the in-plane spin polarization is asymmetric between the two elongated surface hole pockets across the zone center. Moreover, we uncovered a giant out-of-plane spin polarization as large as the in-plane counterpart which switches the sign across the Γ-M line. We discuss the present finding in terms of the symmetry breaking and the many-body effects.     

Unusual Fragmentation of Peptide and Protein in Matrix-assisted Laser Desorption/lonization Mass Spectrometry

Unusual amine - bond fragmentation on the peptide/protein backbone has been reported using matrix - assisted laser desorption/ionization time - of- flight mass spectrometry (MALDI - TOFMS)The amine - bond cleavage occurred without metastable decay, while the peptide - bond cleavage occurred with metastable decay of peptide ions in a drift region of TOF mass analyzer. It was presumed that the amine - bond cleavage occurred as a non - ergodic process independent of the ionization under MALDI conditions.     

Projectile acceleration in a single-stage gun at breech pressures below 50 MPa

Experimental studies were carried out to investigate projectile acceleration in a single-stage gun at breech pressures below 50 MPa. The gun was driven by firing either liquid or solid propellant. In-bore projectile velocity was continuously recorded using the well-known, precise VISAR interferometer technique so that accurate projectile acceleration data could be deduced. Both the attained projectile acceleration and muzzle exit velocity depend upon the charge-to-mass ratio and the pressure at which the blow-out disk ruptures. The results obtained from these experiments render information on the interplay between propellant combustion and projectile acceleration for low in-bore pressure regimes, and they provide the input data required for adequate numerical simulation.     

Analysis of oxidation process of cholecystokinin octapeptide with reactive oxygen species by high‐performance liquid chromatography and subsequent electrospray ionization mass spectrometry

The C‐terminal octapeptide of cholecystokinin (CCK8) includes some easily oxidizable amino acids. The oxidation of CCK8 by reactive oxygen species (ROS) such as hydrogen peroxide (H₂O₂) and hydroxyl radicals (OH^?) was investigated using reversed‐phase high performance liquid chromatography (RP‐HPLC) and subsequent electrospray ionization mass spectrometry. The mechanism of oxidation of CCK8 in the H₂O₂ system differed from that of CCK8 in the Fenton system, in which OH^? are produced. In the H₂O₂ system, ²⁸Met and ³¹Met were oxidized to methionine sulfoxide, and no further oxidation or degradation/hydrolysis occurred. On the other hand, in the Fenton system, ²⁸Met and ³¹Met residues were oxidized to methionine sulfone via the formation of methionine sulfoxide. In addition, the oxidized product was observed at the Trp residue but not at the Tyr residue, and small peptide fragments from CCK8 were observed in the Fenton system. From these results, it was concluded that ²⁸Met and ³¹Met residues of CCK8 are susceptible to oxidation by ROS. Copyright © 2009 John Wiley & Sons, Ltd.     

Direct evidence for degradation of esperamicin A1 with thiol confirmed by fast-atom bombardment mass spectrometry.

A degradation of esperamicin A1, which is a potent antitumor antibiotic having DNA-cleaving activity, was studied by fast-atom bombardment (FAB) mass spectrometry. It was proved that the degradation easily occurs via the thiol group(s) in the matrix solution and not by a FAB-induced reaction. It was concluded that from the FAB mass spectra of all non-volatile compounds, the molecular weight should be determined by using at least two chemically different matrices.     

On the stable posture of a pair of parallel cylinders in a uniform flow *

The stable posture of a pair of parallel circular cylinders in a uniform flow was experimentally studied when it was free to rotate about an axis at the middle of the two cylinders. The cylinder pair comes to rest facing the oncoming flow side by side, the line connecting the centers of the two cylinders being perpendicular to the flow, when s/d = 0.5, where s is the distance between the center of rotation and the central axis of each cylinder and d is the diameter of the cylinder. When s/d = 1.0 or 1.5, the cylinder pair is stable both in tandem, with one cylinder behind the other, and in side-by-side arrangements to the oncoming flow. When s/d 2.0, the cylinder pair is stable only in tandem arrangements.     

Axisymmetric shock wave interaction with a cone: a benchmark test

Results of the benchmark test are presented of comparing numerical schemes solving shock wave of M_s = 2.38 in nitrogen and argon interacting with a 43∘ semi-apex angle cone and corresponding experiments. The benchmark test was announced in Shock Waves Vol. 12, No. 4, in which we tried to clarify the effects of viscosity and heat conductivity on shock reflection in conical flows. This paper summarizes results of ten numerical and two experimental applications. State of the art in studies regarding the shock/cone interaction is clarified. PACS 01.50.Kw, 47.15.Pn Communicated by K. Takayama     

Stability of naturally occurring pyrazines and construction route of pyrazine rings

Naturally occurring pyrazines fit well the theory that conformity to the TCS rule gives a stable molecular system. Thus, many pyrazines so far synthesized and those in nature which are energetically very stable molecules can be synthetically quite accessible. The TCS rule applies very well to the construction route of pyrazine rings.