Novel Technique for All-Optical Clock Extraction Using Fiber Bragg Gratings

We demonstrate a simple passive technique, using phase shifted fibre Bragg gratings, for extraction of optical clock signals from RZ optical data signals . The generation of an optical clock signal at 12.5 GHz from a 12.5 Gbs RZ optical data stream is experimentally demonstrated with simulation of optical clock extraction at 10 GHz fro m 40 Gbs OTDM data streams .     

Cycloalkene budding: mass spectrometric studies of competitive and dual cycloalkene extrusion reactions from doubly unsaturated aldehyde N,N-dimethylhydrazones

Mass spectral fragmentation pathways of four doubly unsaturated aldehyde N,N-dimethylhydrazones were investigated using EI-MS and tandem mass spectrometry (MS/MS) under electron ionization and collisionally activated decomposition (CAD) conditions. Cyclopentene extrusion was found to be slightly favored over cyclohexene loss in a hydrazone capable of losing either cycloalkene. Evidence for the regeneration of a chain-shortened iminium radical cation as a result of cycloalkene extrusion was provided by studying substrates capable of undergoing successive cycloalkene budding sequences. EI-MS of these compounds shows sequential loss of both cyclopentene and cyclohexene, in accord with expectations for a cascade mechanism. Although these MS/MS experimental results are also compatible with alternative mechanisms which would entail the simultaneous loss of both neutral cycloalkenes or of a macrocyclic diene, a rapid cascade of cycloalkene budding accounts best for the experimental observations.     

Preparation and properties of aromatic polyamides and copolyamides from phenylindanedicarboxylic acid and aromatic diamines

Aromatic polyamides (aramids) having inherent viscosities of 0.5–1.10 dL/g were prepared by the direct polycondensation of 1,1,3-trimethyl-3-(4-carboxyphenyl)indane-5-carboxylic acid with various aromatic diamines using triphenyl phosphite and pyridine as the condensing agents. Copolyamides were also prepared by a similar procedure from a mixture of the phenylindane diacid, terephthalic acid, and p-phenylenediamine. Almost all of the aramids were soluble in a variety of solvents such as N-methyl-2-pyrrolidone, pyridine, and m-cresol, and afforded transparent and tough films by the solution casting. These aramids and copolyamides had glass transition temperatures in the range of 290–355°C, and started to lose weight at 340°C in air.     

Desorption ionization by charge exchange (DICE) for sample analysis under ambient conditions by mass spectrometry

An ambient pressure ionization technique for mass spectrometric analysis of substances present on solid surfaces was developed. A nebulized spray containing molecular ions of a solvent such as toluene can be generated by passing the solvent through a stainless steel capillary held at a high voltage. When the stream of charged droplets produced in this way is directed onto a solid surface, the analytes present on the surface are desorbed and ionized by a charge exchange process. This technique was shown to desorb and generate positively charged molecular ions from compounds that are not readily ionized by some other ambient methods, under positive-ion generation mode. For example, intense signals representing radical cations of 1,4-hydroquinone, limonene, thymol, and several other compounds were observed when the analytes were deposited on a metal surface and exposed to a toluene spray nebulized from the metal capillary maintained at a potential of about +5 kV. In contrast, when the same samples were exposed to a spray of water/methanol/formic acid under customary DESI-like (positive-ion mode) conditions, no peaks representing the analytes were observed.     

Elemental sulfur as a versatile low-mass-range calibration standard for laser desorption ionization mass spectrometry

Facile generation of series of singly charged radical anions (S _n ^−· ; n=1–15) and cations (S _n ^+· ; n=2–11) by direct laser ionization renders elemental sulfur an excellent material for the low-mass-region calibration of time of flight (TOF) mass spectrometers. Upon irradiation by a 337-nm UV laser, elemental sulfur undergoes facile ionization without the need of an additional laser-absorbing matrix. An intense and evenly spaced set of peaks is obtained in both modes.     

Oxidative Ionization Under Certain Negative-Ion Mass Spectrometric Conditions

1,4-Hydroquinone and several other phenolic compounds generate (M – 2) ^–? radical-anions, rather than deprotonated molecules, under certain negative-ion mass spectrometric conditions. In fact, spectra generated under helium-plasma ionization (HePI) conditions from 1,4-hydroquinone and 1,4-benzoquinone (by electron capture) were practically indistinguishable. Because this process involves a net loss of H^? and H⁺, it can be termed oxidative ionization. The superoxide radical-anion (O₂ ^–?), known to be present in many atmospheric-pressure plasma ion sources operated in the negative mode, plays a critical role in the oxidative ionization process. The presence of a small peak at m/z 142 in the spectrum of 1,4-hydroquinone, but not in that of 1,4-benzoquinone, indicated that the initial step in the oxidative ionization process is the formation of an O₂ ^–? adduct. On the other hand, under bona fide electrospray ionization (ESI) conditions, 1,4-hydroquinone generates predominantly an (M – 1) ^– ion. It is known that at sufficiently high capillary voltages, corona discharges begin to occur even in an ESI source. At lower ESI capillary voltages, deprotonation predominates; as the capillary voltage is raised, the abundance of O₂ ^–? present in the plasma increases, and the source in turn increasingly behaves as a composite ESI/APCI source. While maintaining post-ionization ion activation to a minimum (to prevent fragmentation), and monitoring the relative intensities of the m/z 109 (due to deprotonation) and 108 (oxidative ionization) peaks recorded from 1,4-hydroquinone, a semiquantitative estimation of the APCI contribution to the overall ion-generation process can be obtained.

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Graphical Abstract ?

     

Mild route to generate gaseous metal anions

Gaseous metal anions such as Na(-), K(-), Cs(-), and Ag(-) can be generated at ambient temperatures by the collision-induced dissociation of the anions of several dicarboxylic acid salts, including oxalate, maleate, fumarate, succinate, and glutamate salts. The formation of gaseous metal anions in this way is unprecedented because the metal is initially present in its cationic form. The mild process described here could facilitate novel applications of metal anions as selective reagents for gas-phase ion-molecule and ion-ion reactions. Ab initio calculations were used to describe the dissociation process for anions of the oxalate salts. The formation of alkalides occurs via production of a metal-carbon dioxide anion intermediate with a bidentate three-center two-electron bond to the metal. The metal atom acquires a partial negative charge in the intermediate structure.     

Localization of Fatty Acyl and Double Bond Positions in Phosphatidylcholines Using a Dual Stage CID Fragmentation Coupled with Ion Mobility Mass Spectrometry

A high content molecular fragmentation for the analysis of phosphatidylcholines (PC) was achieved utilizing a two-stage [trap (first generation fragmentation) and transfer (second generation fragmentation)] collision-induced dissociation (CID) in combination with travelling-wave ion mobility spectrometry (TWIMS). The novel aspects of this work reside in the fact that a TWIMS arrangement was used to obtain a high level structural information including location of fatty acyl substituents and double bonds for PCs in plasma, and the presence of alkali metal adduct ions such as [M?+?Li]⁺ was not required to obtain double bond positions. Elemental compositions for fragment ions were confirmed by accurate mass measurements. A very specific first generation fragment ion m/z 577 (M-phosphoryl choline) from the PC [16:0/18:1 (9Z)] was produced, which by further CID generated acylium ions containing either the fatty acyl 16:0 (C₁₅H₃₁CO⁺, m/z 239) or 18:1 (9Z) (C₁₇H₃₃CO⁺, m/z 265) substituent. Subsequent water loss from these acylium ions was key in producing hydrocarbon fragment ions mainly from the α-proximal position of the carbonyl group such as the hydrocarbon ion m/z 67 (+H₂C-HC?=?CH-CH?=?CH₂). Formation of these ions was of important significance for determining double bonds in the fatty acyl chains. In addition to this, and with the aid of ¹³C labeled lyso-phosphatidylcholine (LPC) 18:1 (9Z) in the ω-position (methyl) TAP fragmentation produced the ion at m/z 57. And was proven to be derived from the α-proximal (carboxylate) or distant ω-position (methyl) in the LPC.