“Meta Elimination,” a Diagnostic Fragmentation in Mass Spectrometry

The diagnostic value of the “ortho effect” for unknown identification by mass spectrometry is well known. Here, we report the existence of a novel “meta effect,” which adds to the repertoire of useful mass spectrometric fragmentation mechanisms. For example, the meta-specific elimination pathway described in this report enables unequivocal identification of meta isomers from ortho and para isomers of carboxyanilides. The reaction follows a specific path to eliminate a molecule of meta-benzyne, from the anion produced after the initial decarboxylation of the precursor. Consequently, in the CID spectra of carboxyanilides, a peak for the (R-CO-NH)^– anion is observed only for the meta isomers. For example, the peaks observed at m/z 58, 86, 120, 128, and 170 from acetamido-, butamido-, benzamido, heptamido-, and decanamido-benzoates, respectively, were specific only to the spectra of meta isomers.     

Hydroxycarbonyl anion (m/z 45), a diagnostic marker for α‐hydroxy carboxylic acids

Collision‐induced dissociation mass spectra of anions derived from α‐hydroxy carboxylic acids (AHAs) show a diagnostic peak at m/z 45. Product ion spectra recorded from this m/z 45 ion confirm that it represents the hydroxycarbonyl anion ( ), and not the formate anion ( ) as sometimes described in the literature. For example, the formate anion is not only defiant to further fragmentation but is also unreactive toward CO₂. In contrast, the hydroxycarbonyl anion easily fragments to produce a peak at m/z 17 for the hydroxyl anion, and also readily reacts with CO₂ to produce a peak at m/z 61 for the bicarbonate anion. The hydrogen atom in the hydroxycarbonyl anion and that in the formate anion are not mobile within the skeletal framework of the ions, since the two ions did not manifest any interconversion under the conditions and time scales of our mass spectrometric experiments. The other significant product ion peak in the spectra of deprotonated AHAs represents a 46‐Da loss. MS/MS data from appropriately deuteriated compounds confirmed that one hydrogen atom from the C‐2 position, and the other from the hydroxy group are specifically removed for this loss of elements of formic acid. Moreover, the two oxygen atoms eliminated for the HCOOH loss originate exclusively from the carboxylate group. Copyright © 2008 John Wiley & Sons, Ltd.     

CBS-4 ab initio results on the formation and stability of N-aminoazetidine radical cation and derivatives

Experimental evidence has recently indicated the role of substituted azetidine radical cations in the electron ionization mass spectrometric fragmentation of N,N-dimethyltydrazone derivatives of 5- and 6-unsaturated straight-chain aldehydes. Although the 2+2 cycloaddition of ethylene and methyleneamine to form neutral azetidine has a very high energy barrier and is only mildly exothermic, CBS-4 ab initio calculations show that formation of the proposed radical cation intermediate is strongly exothermic with a low barrier. Further calculations show that the general energetics remain essentially unchanged even when substituents of the type present in the mass spectrometric studies are included. These calculations demonstrate that the proposed new mass spectral fragmentation mechanism is both thermodynamically and kinetically feasible.     

Formation of Carbamate Anions by the Gas-phase Reaction of Anilide Ions with CO<Subscript>2</Subscript>

The anilide anion (m/z 92) generated directly from aniline, or indirectly as a fragmentation product of deprotonated acetanilide, captures CO₂ readily to form the carbamate anion (m/z 136) in the collision cell, when CO₂ is used as the collision gas in a tandem-quadrupole mass spectrometer. The gas-phase affinity of the anilide ion to CO₂ is significantly higher than that of the phenoxide anion (m/z 93), which adds to CO₂ only very sluggishly. Our results suggest that the efficacy of CO₂ capture depends on the natural charge density on the nitrogen atom, and relative nucleophilicity of the anilide anion. Generally, conjugate bases generated from aniline derivatives with proton affinities (PA) less than 350 kcal/mol do not tend to add CO₂ to form gaseous carbamate ions. For example, the anion generated from p-methoxyaniline (PA = 367 kcal/mol) reacts significantly faster than that obtained from p-nitroaniline (PA = 343 kcal/mol). Although deprotonated p-aminobenzoic acid adds very poorly because the negative charge is now located primarily on the carboxylate group, it reacts more efficiently with CO₂ if the carboxyl group is esterified. Moreover, mixture of CO₂ and He as the collision gas was found to afford more efficient adduct formation than CO₂ alone, or as mixtures made with nitrogen or argon, because helium acts as an effective “cooling” gas and reduces the internal energy of reactant ions.

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Performance of developed natural vein graphite as the anode material of rechargeable lithium ion batteries

Electrochemical performance of natural vein graphite as an anode material for the rechargeable Li-ion battery (LIB) was investigated in this study. Natural graphite exhibits many favorable characteristics such as, high reversible capacity, appropriate potential profile, and comparatively low cost, to be an anode material for the LIB. Among the natural graphite varieties, the vein graphite typically possesses very high crystallinity together with extensively high natural purity, which in turn reduces the cost for purification. The developed natural vein graphite variety used for this study, possessed extra high purity with modified surface characteristics. Half-cell testing was carried out using CR 2032 coin cells with natural vein graphite as the active material and 1 M LiPF₆ (EC: DMC; vol. 1:1) as the electrolyte. Galvanostatic charge–discharge, cyclic voltammetry, and impedance analysis revealed a high and stable reversible capacity of 378 mA h g^?1, which is higher than the theoretical capacity (372 mA h g^?1 for LiC₆). Further, the observed low irreversible capacity acquiesces to the high columbic efficiency of over 99.9%. Therefore, this highly crystalline developed natural vein graphite can be presented as a readily usable low-cost anode material for Li-ion rechargeable batteries.     

Fabrication and optimization of single-junction nc-Si:H n–i–p solar cells using Si:H phase diagram concepts developed by real time spectroscopic ellipsometry

In this study, we have developed and applied deposition phase diagrams in the plane of the bulk layer thickness d_b and the H₂-dilution ratio R = [H₂]/[Si₂H₆] for Si:H materials deposited by 70 MHz VHF PECVD from [H₂] + [Si₂H₆] mixed gases on c-Si/(native-oxide)/n-layer substrates. To establish the phase diagrams, series of Si:H depositions having different R values over the range of 60–150 were measured in real time using a rotating-compensator multichannel ellipsometer. Using phase diagram concepts for guidance, we have fabricated high efficiency single-junction nc-Si:H n–i–p solar cells with ～3 Å/s intrinsic layers using the VHF PECVD process. We have found that the nc-Si:H solar cells with the best performance are obtained by incorporating i-layers deposited in the single-phase nanocrystalline silicon regime near the transition boundary to mixed-phase (a + nc)-Si:H. Applying insights from real time spectroscopic ellipsometry moreover, we have investigated in detail the effects of the phase of the underlying n-layer on the phase evolution of the overdeposited Si:H i-layer and on the overall device performance. With the strategy developed here, a stabilized efficiency of η = 9.46% (V_oc = 0.516 V, J_sc = 24.65 mA/cm², FF = 0.744) has been achieved for nc-Si:H solar cells (0.25 cm² in active area) fabricated with an i-layer deposition rate of ～2.2 Å/s.     

Collision‐induced dissociation mass spectra of glucosinolate anions

Collision‐induced dissociation (CID) mass spectra of differently substituted glucosinolates were investigated under negative‐ion mode. Data obtained from several glucosinolates and their isotopologues (³⁴S and ²H) revealed that many peaks observed are independent of the nature of the substituent group. For example, all investigated glucosinolate anions fragment to produce a product ion observed at m/z 195 for the thioglucose anion, which further dissociates via an ion/neutral complex to give two peaks at m/z 75 and 119. The other product ions observed at m/z 80, 96 and 97 are characteristic for the sulfate moiety. The peaks at m/z 259 and 275 have been attributed previously to glucose 1‐sulfate anion and 1‐thioglucose 2‐sulfate anion, respectively. However, based on our tandem mass spectrometric experiments, we propose that the peak at m/z 275 represents the glucose 1‐thiosulfate anion. In addition to the common peaks, the spectrum of phenyl glucosinolate (β‐D ‐Glucopyranose, 1‐thio‐, 1‐[N‐(sulfooxy)benzenecarboximidate] shows a substituent‐group‐specific peak at m/z 152 for C₆H₅‐C(?NOH)S^?, the CID spectrum of which was indistinguishable from that of the anion of synthetic benzothiohydroxamic acid. Similarly, the m/z 201 peak in the spectrum of phenyl glucosinolate was attributed to C₆H₅‐C(?S)OSO₂^?. Copyright © 2009 John Wiley & Sons, Ltd.     

Discrete approximations to real-valued leaf sequencing problems in radiation therapy

For a given m×n nonnegative real matrix A, a segmentation with 1-norm relative error e is a set of pairs (α,S)={(α₁,S₁),(α₂,S₂),…,(α_k,S_k)}, where each α_i is a positive number and S_i is an m×n binary matrix, and , where |A|₁ is the 1-norm of a vector which consists of all the entries of the matrix A. In certain radiation therapy applications, given A and positive scalars γ,δ, we consider the optimization problem of finding a segmentation (α,S) that minimizes subject to certain constraints on S_i. This problem poses a major challenge in preparing a clinically acceptable treatment plan for Intensity Modulated Radiation Therapy (IMRT) and is known to be NP-hard. Known discrete IMRT algorithms use alternative objectives for this problem and an L-level entrywise approximation (i.e. each entry in A is approximated by the closest entry in a set of L equally-spaced integers), and produce a segmentation that satisfies . In this paper we present two algorithms that focus on the original non-discretized intensity matrix and consider measures of delivery quality and complexity (∑α_i+γk) as well as approximation error e. The first algorithm uses a set partitioning approach to approximate A by a matrix that leads to segmentations with smaller k for a given e. The second algorithm uses a constrained least square approach to post-process a segmentation of to replace with real-valued α_i in order to reduce k and e.     

Untrapping Kinetically Trapped Ions: The Role of Water Vapor and Ion-Source Activation Conditions on the Gas-Phase Protomer Ratio of Benzocaine Revealed by Ion-Mobility Mass Spectrometry

The role of water vapor in transforming the thermodynamically preferred species of protonated benzocaine to the less favored protomer was investigated using helium-plasma ionization (HePI) in conjunction with ion-mobility mass spectrometry (IM-MS). The IM arrival-time distribution (ATD) recorded from a neat benzocaine sample desorbed to the gas phase by a stream of dry nitrogen and ionized by HePI showed essentially one peak for the O-protonated species. However, when water vapor was introduced to the enclosed ion source, within a span of about 150 ms the ATD profile changed completely to one dominated by the N-protonated species. Under spray-based ionization conditions, the nature and composition of the solvents have been postulated to play a decisive role in defining the manifested protomer ratios. In reality, the solvent vapors present in the ion source (particularly the ambient humidity) indirectly dictate the gas-phase ratio of the protomers. Evidently, the gas-phase protomer ratio established at the confinement of the ions is readjusted by the ion-activation that takes place during the transmission of ions to the vacuum. Although it has been repeatedly stated that ions can retain a “memory” of their solution structures because they can be kinetically trapped, and thereby represent their solution-based stabilities, we show that the initial airborne ions can undergo significant transformations in the transit through the intermediate vacuum zones between the ion source and the mass detector. In this context, we demonstrate that the kinetically trapped N-protomer of benzocaine can be untrapped by reducing the humidity of the enclosed ion source.

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