Product ion spectral simplification using time-delayed fragment ion capture with tandem linear ion traps

A new technique to generate product ion spectra as the internal energy of a collisionally activated precursor ion evolves is described. The precursor ion is activated by acceleration into a mass-selective linear ion trap under conditions whereby some of the fragment ions formed are unstable within the trap. After a time delay the stability parameters of the ion trap are changed to allow capture of fragments that that were previously unstable. The result is a product ion spectrum that originates from precursor ions with a modified internal energy distribution. It is possible to follow the evolution of the precursor internal energy distribution for many milliseconds after admittance of the precursor ions into the linear ion trap. Time-delayed fragmentation product ion spectra typically display reduced sequential fragmentation products leading to spectra that are more easily interpreted. Several important experimental parameters important to time-delayed fragmentation have been identified and are discussed. The technique has applications for both small precursor ions and multiply charged peptides.     

Mutual storage mode ion/ion reactions in a hybrid linear ion trap

Ion/ion proton transfer reactions involving mutual storage of both ion polarities in a linear ion trap (LIT) that comprises part of a hybrid triple quadrupole/linear ion trap mass spectrometer have been effected. Mutual ion storage in the x- and y-dimensions arises from the normal operation of the oscillating quadrupole field of the quadrupole array, while storage in the z-dimension is enabled by applying unbalanced radio-frequency amplitudes to opposing sets of rods of the array. Efficient trapping (>90%) is achieved for thermalized ions over periods of several seconds. Reactions were demonstrated for multiply charged protein/peptide cations formed by electrospray with anions derived from glow discharge ionization of perfluoro(methyldecalin) (PMD) introduced from the side of the LIT rod array. Doubly and singly charged protein ions are readily formed via ion/ion reactions. The parameters that affect ion/ion reactions are discussed, including the degree of RF unbalance on the LIT rods, vacuum pressure, nature of the buffer gas, reaction time, anion abundance, and the low mass cutoff for ion/ion reaction. The present system has a demonstrated upper mass-to-charge ratio limit of at least 33,000. The system also has high flexibility with respect to defining MS(n) experiments involving both collision-induced dissociation (CID) and ion/ion reactions. Experiments are demonstrated involving beam-type CID in the pressurized collision quadrupole (Q2) followed by ion/ion reactions involving the product ions in the LIT. Ion parking experiments are also demonstrated using the mutual storage ion/ion reaction mode in the LIT, with a parking efficiency over 60%.     

Tunable and coherent radiation in the VUV: high efficiency four-wave difference-frequency mixing in xenon

We report a novel source of tunable, coherent radiation in the vacuum ultraviolet, which use resonantly enhanced difference-frequency mixing in xenon gas Efficiencies are high (o.4%) at modest input laser intensities. With existing dye lasers the range of tunability will span the 152–200 nm region.     

Synthesis and characterization of polymethacrylates containing conjugated oligo(phenylene ethynylene)s as side chains

In order to form suitable systems designed for resonance energy transfer, a series of monodisperse methacrylate‐based monomers containing rigid π‐conjugated oligo(phenylene ethynylenes) with different sizes of the conjugated systems ( M1 – M3 ), and therefore different optoelectronic properties, were synthesized and subsequently polymerized using the reversible addition–fragmentation chain transfer polymerization technique ( P1 – P3 ). In addition, these oligomers were also copolymerized with methyl methacrylate. The obtained polymers were characterized by ¹H NMR spectroscopy, size exclusion chromatography, and analytical ultracentrifugation. The photophysical properties of the polymers were studied by UV–vis absorption and emission spectroscopy in diluted solutions as well as in thin films and compared to the photophysics of the corresponding monomers. Thereby, changes going from monomeric to polymeric systems could be detected in fluorescence quantum yields and lifetimes pointing to energy trapping, e.g., energy transfer. Donor–acceptor copolymers containing different numbers of monomeric units within the side chain exhibit differences in the emission spectra, indicating that energy trapping in polymers is very sensitive to structural properties such as the chain length. UV–vis absorption spectroscopy as well as time‐resolved lifetime studies indicate intrapolymer and interpolymer energy transfer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Correspondence between de Saint-Venant and Boussinesq. 1: Birth of the Shallow–Water Equations

The Shallow–Water Equations (SWEs), also referred to as the de Saint-Venant equations, constitute the current governing mathematical tool for free-surface water flows. These include, e.g., flood flows in rivers and in urban zones, flows across hydraulic structures as dams or wastewater facilities, flows in the environmental fields, glaciology, or meteorology. Despite this attractiveness, the system of two partial differential equations has an exact mathematical solution only for a limited number of problems of practical relevance.This historical work on the SWEs is based on a correspondence between two 19th-century scientists, de Saint-Venant and Boussinesq. Their well-known papers are thus commented from the point of development of their theory; the input of both scientists is evidenced by their writings, and comments of both to each other that led to what is commonly known as the SWEs. Given the age difference of the two of 45 years, the experienced engineer de Saint-Venant, and the mathematician Boussinesq, two eminent researchers, met to discuss not only problems in hydraulics, but in physics generally. In addition, their correspondence embraced also questions in ethics, religion, history of sciences, and personal news.The results of the SWEs cease to hold if streamline curvature effects dominate; this includes breaking waves, solitary and cnoidal waves, or non-linear waves in general. In most other cases, however, the SWEs perfectly apply to typical flows in engineering practice; they are considered the fundamental system of equations describing open channel flows. This work thus provides a background to its birth, including lots of comments as to its improvement, physical meanings, methods of solution, and a discussion of the results. This paper also deals with the steady flow equations, gives a short account on the main persons mentioned in the Correspondence, and provides a summary of further developments of the SWEs until 1920.     

SET-induced photorearrangement of 2-phenylallyl phosphites. Stereochemistry at phosphorus. Application to cyclic nucleotide derivatives

The stereochemistry at phosphorus of the SET-induced photorearrangement of diastereomeric 4-tert-butyl-2-phenylallyl-1,3,2-dioxaphosphorinanes (8) to the corresponding 2-phenylallylphosphonates (9), which involves exicted singlet 1,4-dicyanonaphthalene (1DCN*) as one-electron oxidant, was investigated. The rearrangement occurs with close to complete retention of configuration at phosphorus. The previously postulated mechanism for this photorearrangement is shown to be consistent with the stereochemical finding. Thus, one-electron reduction by DCN.- of the presumably stereospecifically formed distonic cyclic 1,3-cation radical intermediate 15, generated from cis-8 (Scheme 2), yields the thermodynamically stable diradical 16. beta scission of 16 forms phosphonate cis-9. An alternative mechanism involving beta scission of 15 to a styryl cation radical, prior to one-electron reduction to 15, is discounted on the basis of unpublished trapping studies using MeOH. The direct, kinetically controlled formation of diradical 16 rather than the thermodynamically less stable 21 with CH2 bonded apically to phosphorus is argued to be consistent with the essentially equal values of the quantum yield for phosphonate formation (phi P) on SET-induced rearrangement of the acyclic 2-phenylallyl phosphite 1 and phosphite 7 with phosphorus incorporated in a six-membered (1,3,2-dioxaphosphorinane) ring. This mechanism is contrasted to that for the previously reported triplet-sensitized photorearrangements of phosphites 1 and 7, which have greatly different phi P values. For these reactions, kinetic formation of the triplet analogue of 21, but without the tert-butyl substituent, requires a permutation of substituents for conversion to diradical 16 prior to intersystem crossing and beta scission to form the phosphonate corresponding to 7. The preparative-scale SET-induced photorearrangement of the thymidine-based 2-phenylallyl 3',5'-phosphite 10 gave both diastereomers of phosphonate 11 that were separated by HPLC. The 2-phenylallyl functionality provides an opportunity for further functionalization. As reported elsewhere, 11 was not formed in useful amounts via triplet-sensitized reaction of 10.     

Hysteretic transition between avalanches and continuous flow in rotated granular systems

Experiments in drums or cylinders partly filled with a granular system and rotated constantly about their horizontally aligned axis of symmetry show a hysteretic transition from discrete avalanches to continuous flow if the rotation rate is adiabatically changed. Herein, we show that this hysteresis can be explained by the impact of global Langevin-type fluctuations in a recently proposed minimal model for surface flow along granular piles. For too large magnitudes of the fluctuations corresponding to almost elastic grains, the hysteresis vanishes. This might explain why molecular dynamical simulations were not yet able to detect the hysteretic transition. (c) 1999 American Institute of Physics.     

Dual active sets and constrained optimization

Two dual methods for solving constrained optimization problems are presented: the Dual Active Set algorithm and an algorithm combining an unconstrained minimization scheme, an augmented Lagrangian and multiplier updates. A new preconditioner is introduced that has a significant impact on the speed of convergence.This research was supported by US Army Research Office Contract DAAL03-89-G-0082, and by National Science Foundation Grant DMS-9022899.