Fast-atom bombardment and tandem mass spectrometry of macrolide antibiotics

Molecular weights of macrolide antibiotics can be determined from either (M + H)⁺ or (M + Met)⁺, the latter desorbed from alkali metal salt-saturated matrices. The ion chemistry of macrolides, as determined by tandem mass spectrometry (MS/MS), is different for ions produced as metallated than those formed as (M + H)⁺ species. An explanation for these differences is the location of the charge. For protonated species, the charge is most likely situated on a functional group with high proton affinity, such as the dimethylamino group of the ammo sugar. The alkali metal ion, however, is bonded to the highly oxygenated aglycone. As a result, the collision-activated dissociation spectra of protonated macrolides are simple with readily identifiable fragment ions in both the high and low mass regions but no fragments in the middle mass range. In contrast, the cationized species give complex spectra with many abundant ions, most of which are located in the high mass range. The complementary nature of the fragmentation of these two species recommends the study of both by MS/MS when determining the structure or confirming the identity of these biomaterials.     

High pressure trapping in Fourier transform mass spectrometry: A radiofrequency-only-mode event

A new event for the Fourier transform mass spectrometry (FTMS) sequence is developed and demonstrated. During this event, called a radiofrequency (RF)-only mode event, the typical passive cubic trap of a Fourier transform mass spectrometer is made to operate as an active quadrupole ion trap. The transition between active and passive modes is developed so that ion loss as a consequence of the transition can be held to 15% or less. The adduct of the ion-molecule reaction of the 1,3-butadiene radical cation and methyl vinyl ether was detected during the Rf-only-mode event at a helium pressure of ～1×10^?3 torr even though this adduct is not detectable under standard FTMS operating conditions.     

A Mechanism for Poor High Mass Performance in Fourier Transform Mass Spectrometry

The discovery of a mass-dependent electrical mechanism for signal loss of high mass ions in Fourier transform mass spectrometry is reported. Theoretical calculations and experimental evidence show the existence of resonances involving the z-motion and radial motion of the ion. The resonances are intrinsic in the cubic trap. This results in energy transfer between modes, expansion of the ion cloud, and a corresponding loss of signal. Quadrupolar trapping potential wells are proposed as a solution.     

Ion cloud manipulation using the radiofrequency-only-mode as an improvement for high mass detection in fourier transform mass spectrometry

It has been difficult to achieve the expected high resolving power for high-mass biomolecule ions in Fourier transform mass spectrometry. Our hypothesis is that ion clouds produced by laser desorption or injection are diffuse and produce poor signals. To test the hypothesis, clouds of benzene molecular ions produced by electron ionization were purposefully expanded via magnetron mode excitation and characterized by a new experimental sequence for cloud sectional analysis. The expanded cloud was then successfully focused to the trap center by using a high-pressure dynamic event (radiofrequency-only mode). The expanded cloud in a conventional cubic trap produces no detectable signal, whereas the focused cloud in a compensated trap yields a high-resolution signal with good signal-to-noise ratio.     

Broadly tunable dual-wavelength light source for coherent anti-Stokes Raman scattering microscopy

The signal and idler beams from a picosecond, synchronously pumped optical parametric oscillator (OPO) provide the two colors necessary for coherent anti-Stokes Raman scattering (CARS) microscopy. The OPO provides a continuously tunable frequency difference between the two beams over a broad range of Raman shifts (100-3700 cm(-1)) by varying the temperature of a single nonlinear crystal. The near-infrared output (900-1300 nm) allows for deep penetration into thick samples and reduced nonlinear photodamage. Applications of this light source to in vivo cell and ex vivo tissue imaging are demonstrated.     

DFT study of NH3 dissociation on Si(1 1 1)-7 × 7. The role of intermolecular interactions

The adsorption of NH₃ molecule on the Si(1 1 1)-7 × 7 surface modelled with a cluster has been studied using density functional theory (DFT). The results indicate the existence of a precursor state for the non-dissociative chemisorption. The active site for the molecular chemisorption is the adatom; while the NH₃ molecule adsorbs on the Si restatom via this preadsorbed state, the adsorption on the Si adatom is produced practically without an energy barrier. The ammonia adsorption on the adatom induces an electron transfer from the dangling bond of this atom to the dangling bond of the adjacent Si restatom, hindering this site for the adsorption of a second NH₃ incoming molecule. However, this second molecule links strongly by means of two H-bonds. The dissociative chemisorption process was studied considering one and two ammonia molecules. For the dissociation of a lonely NH₃ molecule an energy barrier of ∼0.3 eV was calculated, yielding NH₂ on the adatom and H on the restatom. When two molecules are adsorbed, the NH₃-NH₃ interaction yields the weakening of a N-H bond of the ammonia molecule adsorbed closer the Si surface. As a consequence, the dissociation barrier practically disappears. Thus, the presence of a second NH₃ molecule at the adatom-restatom pair of the Si(1 1 1)-7 × 7 surface makes the dissociative reaction self-assisted, the total adsorption process elapsing with a negligible activation barrier (less than 0.01 eV).     

Rabi flopping induces spatial demixing dynamics

We experimentally investigate the mixing and demixing dynamics of Bose-Einstein condensates in the presence of a linear coupling between two internal states. The observed amplitude reduction of the Rabi oscillations can be understood as a result of demixing dynamics of dressed states as experimentally confirmed by reconstructing the spatial profile of dressed state amplitudes. The observations are in quantitative agreement with numerical integration of coupled Gross-Pitaevskii equations without free parameters, which also reveals the criticality of the dynamics on the symmetry of the system. Our observations demonstrate new possibilities for changing effective atomic interactions and studying critical phenomena.     

Covariant Spectator Theory: Foundations and Applications

We provide a short overview of the covariant spectator theory and its applications. The basic ideas are introduced through the example of a ${\phi^4}$ -type theory. High-precision models of the two-nucleon interaction are presented and the results of their use in calculations of properties of the two- and three-nucleon systems are discussed. A short summary of applications of this framework to other few-body systems is also presented.     

Charge transfer prior to fusion

Zeitschrift für Physik A Hadrons and nuclei - In reactions between very asymmetric projectile-target systems charge is preferably transferred from the lighter to the heavier nucleus. This...