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Gas-phase addition of dioxygen to certain ions is a well-known phenomenon in mass spectrometry. For this reaction to occur, the presence of a distonic radical site on the precursor ion is thought to be a prerequisite. Herein, we report that oxygen adduct formation can take place also with deprotonated hydroquinone, which in fact is an even-electron species without a radical site. When the product-ion spectrum of the

Deciphering metabolomic networks has been demonstrated to provide valuable information for diagnosing and monitoring diseases. Herein, we report a technique to monitor untargeted urine metabolites to evaluate prostate cancer aggressiveness and treatment outcome. Direct chemical profiling of urine was achieved by a combined procedure of hyphenating laser diode thermal desorption with atmospheric pressure chemical ionization mass spectrometry (LDTD-APCI-MS). We describe a conceptually new approach to monitoring preoperative urinary metabolic alterations associated with prostate cancer recurrence. By evaluating mass/charge (

Upon collisional activation under mass spectrometric conditions, protonated 2-, 3-, and 4-iodoanilines lose an iodine radical to generate primarily dehydroanilinium radical cations (m/z 93), which ...

The ortho, meta, and para isomers of hydroxybenzyl alcohol can be unequivocally distinguished by the collision-induced dissociation mass spectra of their anions. The presence of a prominent peak at m/z 121 for an elimination of a dihydrogen molecule renders the ortho-isomer spectrum markedly different from those of its meta and para congeners. Investigations carried out with deuterium-labeled isotopologues of the ortho isomer verified that the labile hydrogen atom on the hydroxyl group and one of the benzylic hydrogen atoms are specifically removed in the formation of the m/z 121 ion. The ortho-isomer spectrum also showed a prominent peak at m/z 93. Experimental data indicated that the m/z 93 product ion originates either from a two-step H

Samples of elemental copper, upon laser irradiation under negative-ion LDI-MS conditions, do not generate noticeable signals for copper-bearing gaseous ions. In contrast, a several thousand-fold enhancement of the generated ion current was observed when freshly made mixtures of copper and sulfur powders were laser-ablated. Time-of-flight mass spectra recorded showed a range of peaks with m/z ratios extending to over m/z 8000, indicating the formation in situ of an array of Cu–S ion clusters by a chemical reaction that takes place between the two elements upon laser irradiation. Evidently, sulfur acts as a potent reactive matrix and generates at least three distinguishable series of ion clusters: Cu1Sx− (x = 2, 3, 4…), Cu2Sy− (y = 3, 4, 5…), and Cu3Sz− (z = 3, 4, 5…). Laser ablation of CuS alone did not produce signals beyond m/z 600. Some of the high-mass ions formed in this manner were isobaric; consequently, composite peaks were observed under low-resolution MS conditions. Under high-resolution conditions, however, we were able to separate and determine the composition of some isobaric mixtures. For example, the peak recorded at m/z 287 was resolved to two peaks that represented primarily the 63Cu265Cu32S3− and 63Cu32S7− ions. Intriguingly, the spectra recorded from many copper-containing minerals mixed with sulfur were remarkably similar to those acquired from copper-and-sulfur mixtures, which demonstrated that elemental sulfur has the ability to extract chemically bound copper even from its compounds, and form gas-phase Cu–S clusters of varying composition.

Carbon-fiber aluminum honeycomb sandwich panels are vulnerable to low-velocity impacts, which can cause structural damage and failures that reduce the bearing performance and reliability of the structure. Therefore, a method for locating such impacts through a sensor network is very important for structural health monitoring. Unlike composite laminates, the stress wave generated by an impact is damped rapidly in a sandwich panel, meaning that the signal qualities measured by different sensors vary greatly, thereby making it difficult to locate the impact. This paper presents a method for locating impacts on carbon-fiber aluminum honeycomb sandwich panels utilizing fiber Bragg grating sensors. This method is based on a projective dictionary pair learning algorithm and uses structural sparse representation for impact localization. The measurement area is divided into several sub-areas, and a corresponding dictionary is trained separately for each sub-area. For each dictionary, the sensors are grouped into main sensors within the sub-area and auxiliary sensors outside the sub-area. A balancing weight factor is added to optimize the proportion of the two types of sensor in the recognition model, and the algorithm for determining the balancing weight factor is designed to suppress the negative effects on the positioning of the sensors with poor signal quality. The experimental results show that on a 300 mm × 300 mm × 15 mm sandwich panel, the impact positioning accuracy of this method is 96.7% and the average positioning error is 0.85 mm, which are both sufficient for structural health monitoring.

Ferrocene and its derivatives and nickelocene undergo facile ionization when exposed directly to the ionizing plasma of a helium-plasma ionization (HePI) source. Mass spectra recorded from such samples under ambient positive-ion-generating conditions show intense peaks for the respective molecular ions [M+•] and protonated species [(M + H)+]. The protonation process occurs most efficiently when traces of water are present in the heated nitrogen used as the "heating gas." In fact, the relative population of the two categories of ions generated in this way can be manipulated by regulating the heating-gas flow. Moreover, rapid and highly efficient gas-phase hydrogen-deuterium exchange (HDX) reactions can be performed in the ion source by passing the heating gas through a vial with D2O before it reaches the HePI source. Moreover, the ionized species generated in this way can be subjected to in-source CID fragmentation in the QDa-HePI source very efficiently by varying the sampling-cone voltage. By this procedure, ions generated from ferrocene and nickelocene could be stripped so far as to ultimately generate the bare-metal cation. Other typical fragment-ions produced from protonated metallocenes included the M(cp)1+ ions (M = Fe or Ni), by elimination of a cyclopentadiene molecule, or the molecular cation, by loss of a H• radical. Moreover, H/D exchanges and subsequent tandem mass spectrometric analysis indicated that the central metal core participates in the initial protonation process of ferrocene under HePI conditions. However, in compounds such as ferrocene carboxaldehyde and ferrocene boronic acid, the protonation takes place at the peripheral functional group.

In this work, a scalar Cs magnetometer based on amplitude modulated nonlinear magneto-optical rotation (AM NMOR) is demonstrated and has reached $0.23\ \text{pT}/\sqrt{\text{Hz}}$ at 1 Hz from 10000 nT to 60000 nT. Besides, a scalar potassium magnetometer is experimentally built with totally separated magnetic resonance signals in larger geomagnetic field, where the performance of Cs magnetometer is limited by nonlinear Zeeman effect.

Selected-ion recording (SIR) or multiple-reaction monitoring (MRM) protocols are widely employed for the quantification of targeted analytes by liquid chromatography-mass spectrometry (LC-MS). After chromatographic separation, analytes are desolvated and converted to gaseous ions usually by electrospray-ionization. The chromatographic peaks generated in this way are then integrated for quantification. It is generally assumed that the chromatographic peak intensities are dependent only on the selected MRM-transition protocols and the instrumental parameters set on the mass spectrometer. Using p-aminosalicylic acid (PAS) as a model compound, we demonstrate that the nature of the LC mobile phase exerts a significant effect on the chromatographic peak intensities. Under identical mass spectrometric conditions, chromatographic peak intensities recorded with methanol as the mobile phase were drastically different from those acquired using acetonitrile as the eluent. In fact, the product-ion mass spectra recorded with protonated PAS under different solvent conditions were qualitatively different. The observed differences were attributed to the existence of different protomers of PAS in the gas phase in dissimilar ratios under different solvent-spray conditions. Results from ion-mobility mass spectrometry experiments confirmed this hypothesis. For example, when PAS was sprayed from an acetonitrile solution, the arrival-time profile recorded from the mass-selected m/z 154 ion for protonated PAS showed essentially one arrival-time peak for the N-protonated tautomer. In contrast, the profile recorded from a methanolic PAS solution showed a different arrival-time peak for a more mobile protomer, which was recognized as the carbonyl-protonated PAS. The coexistence of protomers in different and variable ratios in an ensemble of ions generated by electrospray ionization of a single pure compound wields strong ramifications on the identification and quantification of analytes by LC-MS. However, the inclusion of an ion-mobility separator before the mass-selected ions are fragmented and detected by mass spectrometry ameliorates the complications rendered by the coexistence of different protomers and deprotomers.

High-sensitivity total-field atomic magnetometer enables brain-activity measurements in unshielded Earth’s field., Understanding the relationship between brain activity and specific mental function is important for medical diagnosis of brain symptoms, such as epilepsy. Magnetoencephalography (MEG), which uses an array of high-sensitivity magnetometers to record magnetic field signals generated from neural currents occurring naturally in the brain, is a noninvasive method for locating the brain activities. The MEG is normally performed in a magnetically shielded room. Here, we introduce an unshielded MEG system based on optically pumped atomic magnetometers. We build an atomic magnetic gradiometer, together with feedback methods, to reduce the environment magnetic field noise. We successfully observe the alpha rhythm signals related to closed eyes and clear auditory evoked field signals in unshielded Earth’s field. Combined with improvements in the miniaturization of the atomic magnetometer, our method is promising to realize a practical wearable and movable unshielded MEG system and bring new insights into medical diagnosis of brain symptoms.

Upon collisional activation under mass spectrometric conditions, protonated 2-, 3-, and 4-iodoanilines lose an iodine radical to generate primarily dehydroanilinium radical cations (

Insensitive Munition (IM) formulations contain 3-nitro-1,2,4-trizole-5-one (NTO), an energetic compound with the highest aqueous solubility (16 g L−1) among all IM explosives, including 2,4-dinitroanisole (DNAN) and 1-nitroguanidine (NQ); as a result wastewater streams from IM processing facilities can be highly contaminated and potentially toxic. The removal of energetic compounds from wastewater streams prior to their discharge in the environment is imperative, and new technology must be developed to efficiently treat high levels of NTO and other IM compounds in these streams. In this study, the treatment of NTO wastewater by a UV/H2O2 oxidation process under acidic conditions (pH = 3.0 ± 0.1) and a hydrogen peroxide concentration of at least 1500 mg L−1 resulted in successful removal of the energetic compound. The organic carbon from the NTO ring was completely converted to inorganic carbon (CO2), as confirmed through TOC measurements and GC–MS analysis on the reactor headspace. Nitrate and ammonium ions were the major nitrogen by-products, as indicated by mass spectrometry. The results obtained in this work demonstrate that the UV/H2O2 oxidation process can effectively mineralize high concentrations of NTO in wastewater streams leading to recovery of valuable nutrients that can be used for supporting algal biomass growth for biofuel/biogas generation.

Metal-hydride anions of main group elements, such as BaH3– and InH4–, were generated by dissociating formate adducts of the respective metal formates. Upon activation, these adducts fragment by formate-ion ejection or by decarboxylation. For adducts of alkali-metal formates, the formate-ion ejection is the preferred pathway, whereas for those of alkaline-earth and group 13–15 metals, the expulsion of CO2 is the more favorable pathway. Decarboxylation is deemed to yield a metal–hydrogen bond presumably by a hydride transfer to the metal atom. For example, the decarboxylation of Al(η-OCOH)4– and Ga(η-OCOH)4– generated AlH4– and GaH4–, respectively. The initial fragment-ion with a H–M bond formed in this way from adducts of the heavier metals of group 13 (Ga, In, and Tl) undergo a unimolecular reductive elimination, ascribable to the “inert-pair” effect, to lower the metal-ion oxidation state from +3 to +1. As group 13 is descended, the tendency for this reductive elimination process increases. PbH3–, genera...

Singly charged As2n+1 ion clusters (n = 2-11) were generated from elemental arsenic by negative-ion laser-ablation mass spectrometry. The overall abundance of the gaseous As ions generated upon laser irradiation was enhanced nearly a hundred times when As-bearing samples were admixed with sulfur. However, sulfur does not act purely as an inert matrix: irradiating arsenic-sulfur mixtures revealed a novel pathway to generate and detect a series of [AsSn]- clusters (n = 2-6). Intriguingly, the spectra recorded from As2O3, NaAsO2, Na3AsO4, cacodylic acid and 3-amino-4-hydroxyphenylarsonic acid together with sulfur as the matrix were remarkably similar to that acquired from an elemental arsenic and sulfur mixture. This result indicated that arsenic sulfide cluster-ions are generated directly from arsenic compounds by a hitherto unknown pathway. The mechanism of elemental sulfur extracting chemically bound arsenic from compounds and forming [AsSn]- clusters is enigmatic; however, this discovery has a practical value as a general detection method for arsenic compounds. For example, the method was employed for the detection of As in its minerals, and for the imaging of arsenic distribution in minerals such as domeykite. LDI-MS data recorded from a latent image imprinted on a piece of paper from a flat mineral surface, and wetting the paper with a solution of sulfur, enabled the localization of arsenic in the mineral. The distribution of As was visualized as false-color images by extracting from acquired data the relative intensities of m/z 139 (AsS2-) and m/z 171 (AsS3-) ions.

In the past, chrome yellow (lead chromate, PbCrO4 ), a bright orange-red substance, has been widely used as an inorganic pigment in the production of paints, coatings, and plastics. Herein, we demonstrate that laser desorption/ionization mass spectrometry (LDI-MS) is a powerful tool for the detection of lead chromate in solid residues. In fact, lead chromate in trace amounts is easily detectable by LDI-MS even from residues left as latent prints. For example, a latent print obtained by stamping the exposed laterally cut surface of a pencil over 50 years old on an acetonitrile-moistened paper, was successfully imaged for both lead and chromate using a Synapt G2 HDMS mass spectrometer. After rastering the print with a 355 nm laser beam and recording positive- and negative-ion mass spectra over the range m/z 50-1200, we generated false-color 'heat maps' (single-ion images) for 208 Pb+• (m/z 207.98) and Cr2 O6-• (m/z 199.85). The heat maps matched closely with the faint visual image of the pencil imprint. Moreover, our results confirmed that lead chromate was used in the pigment coatings of old pencils. Evidently, LDI-MS imaging is an efficient procedure to survey for the presence of lead and chromate in minerals and other materials. Copyright © 2017 John Wiley & Sons, Ltd.

Metal-hydride anions of main group elements, such as BaH3– and InH4–, were generated by dissociating formate adducts of the respective metal formates. Upon activation, these adducts fragment by formate-ion ejection or by decarboxylation. For adducts of alkali-metal formates, the formate-ion ejection is the preferred pathway, whereas for those of alkaline-earth and group 13–15 metals, the expulsion of CO2 is the more favorable pathway. Decarboxylation is deemed to yield a metal–hydrogen bond presumably by a hydride transfer to the metal atom. For example, the decarboxylation of Al(η-OCOH)4– and Ga(η-OCOH)4– generated AlH4– and GaH4–, respectively. The initial fragment-ion with a H–M bond formed in this way from adducts of the heavier metals of group 13 (Ga, In, and Tl) undergo a unimolecular reductive elimination, ascribable to the “inert-pair” effect, to lower the metal-ion oxidation state from +3 to +1. As group 13 is descended, the tendency for this reductive elimination process increases. PbH3–, generated from the formate adduct of lead formate, reductively eliminated H2 to form PbH–, in which Pb is in oxidation state zero. In the energy-minimized structure [H–Pb(η2-H2)]−, proposed as an intermediate for the process, a H2 molecule is coordinated with PbH– as a dihapto ligand. The formate adducts of strontium and barium produce monoleptic ions such as [M(0)(η2-O2CH)1]−, in which the formate ion is chelated to a neutral metal atom. The bismuth formate adduct undergoes a double reductive elimination process whereby the oxidation state of Bi is reduced from +3 to +1 and then to −1. Upon activation, the initially formed [H–Bi–H]− ion transforms to an anionic η2-H2 complex, which eliminates dihydrogen to form the bismuthide anion (Bi–).

As a kind of structure commonly used in satellite, carbon fiber composite honeycomb sandwich panels are vulnerable to various kinds of damage, especially low-velocity impact damage in the process of using. In this paper, an impact monitoring system based on Fiber Bragg Grating (FBG) sensor is constructed. The frequency domain information of the signal can be obtained by Fourier transform. Monitoring results of different impact points show that the natural frequency of structure is 110Hz and 380Hz, which amplitude of different natural frequency is changed with position of impact point. The energy status of impact response signal can be obtained by wavelet packet analysis. The monitoring results of the same impact point shows that the change of the sensor signal is obvious in thirteenth order and energy size is related to the distance and angle between the impact point and sensor.

There are some biosensors and biochips for the recognition and quantization for particular biological molecules. They are made of conductive polymers and natural biomolecules such as protein, DNA and polysaccharides. The conductive polymers work as electric wires for signal transmission, while the natural biomolecules are receptors. Such electric devices are of complex and heterogeneous structures, in either single chain or condensed chains or dispersive phase separations. In order to investigate the complex structures of the polymer blends in the devices and the relation between the structure and the electrical properties, we have prepared several kinds of nano-structured polyaniline (PANI) with defined aggregate morphologies, i.e., nano-granules or nano-fibers with different aspect ratios. The blends of κ-carrageenan and PANIs have been prepared through sol–gel process. The multi-level structures of PANIs have been characterized with X-ray diffraction (XRD) and scanning electron microscope (SEM). The thermal analysis and dielectric relaxation spectroscopy help to evaluate and to understand the chain relaxation and the interfacial structures of the blends.

Honeycomb structure with high stiffness and light weight is expected to be more applied in the field of morphing wing. We propose a surface reconstruction algorithm based on FBG sensors to reconstruct the surface deformation of honeycomb structure real-timely and rapidly. When flexible honeycomb cores are driven by SMA actuators, the surface curvature monitored by FBG sensing array can be inferred from the changes of central wavelength. According to the surface reconstruction algorithm we proposed, the surface shape can be reconstructed. Composite single-row honeycomb structure specimen consisting of 8 cores, whose cell walls length and thickness is 8mm and 2mm respectively, is bended by electrified SMA actuators into the new steady shape. The experiment shows that the reconstructed surface shape has great agreement with the visual recording surface shape and the error is 5.76% on average.

This paper proposes a quick spectrum scanning and reconstruction method using compressive sensing in composite structure. The strain field of corrugated structure is simulated by finite element analysis. Then the reflect spectrum is calculated using an improved transfer matrix algorithm. The K-means singular value decomposition sparse dictionary is trained . In the test the spectrum with limited sample points can be obtained and the high resolution spectrum is reconstructed by solving sparse representation equation. Compared with the other conventional basis, the effect of this method is better. The match rate of the recovered spectrum and the original spectrum is over 95%.