Structural insights into metal-metalloid glasses from mass spectrometry

Despite being studied for nearly 50 years, smallest chemically stable moieties in the metallic glass (MG) could not be found experimentally. Herein, we demonstrate a novel experimental approach based on electrochemical etching of amorphous alloys in inert solvent (acetonitrile) in the presence of a high voltage (1 kV) followed by detection of the ions using electrolytic spray ionization mass spectrometry (ESI MS). The experiment shows stable signals corresponding to Pd, PdSi and PdSi$_{2}$ ions, which emerges due to the electrochemical etching of the Pd$_{80}$Si$_{20}$ metallic glass electrode. These fragments are observed from the controlled dissolution of the Pd$_{80}$Si$_{20}$ melt-spun ribbon (MSR) electrode. Annealed electrode releases different fragments in the same experimental condition. These specific species are expected to be the smallest and most stable chemical units from the metallic glass which survived the chemical dissolution and complexation (with acetonitrile) process. Theoretically, these units can be produced from the cluster based models for the MG. Similar treatment on Pd$_{40}$Ni$_{40}$P$_{20}$ MSR resulted several complex peaks consisting of Pd, Ni and P in various combinations suggesting this can be adopted for any metal-metalloid glass

Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/. z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/. z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5. ng to 5. μg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2. ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer

Size tuning of Au nanoparticles formed by electron beam irradiation of Au<SUB>25</SUB> quantum clusters anchored within and outside of dipeptide nanotubes

Glutathione protected Au25 quantum clusters, exhibiting characteristic fluorescence, have been uniformly coated inside and outside of &#946;-Ala-L-Ile dipeptide nanotubes. These coated structures have been imaged using the inherent fluorescence of Au25. Upon exposure to an electron beam, in a transmission electron microscope, the quantum clusters gradually transform to gold nanoparticles, of the metallic size regime. The nanoparticles grow to a size of 4.5 nm and thereafter the particle size is unaffected by electron beam exposure. The nanotubes are intact and this template is shown to control the uniformity of the size of the nanoparticles grown. The quantum clusters can be loaded selectively inside the tubes using capillarity of the nanotubes. The sizes of the nanoparticles grown are tuned using electron beam exposure

Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

This is the author’s version of a work that was accepted for publication in Analytica Chimica Acta. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published at: http://dx.doi.org/10.1016/j.aca.2015.01.007Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/. z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/. z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5. ng to 5. μg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2. ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer

Formation of H-2(+) by ultra-low-energy collisions of protons with water ice surfaces

The molecular ion of dihydrogen (H<SUB>2</SUB><SUP>+</SUP>) is produced by 1 eV collisions of protons (H<SUP>+</SUP>) on amorphous water ice surfaces. The reaction is also observed on crystalline ice surfaces, but with lower efficiency. Collisions of D<SUP>+</SUP> on amorphous H<SUP>2</SUP>O and D<SUP>2</SUP>O ices yield D<SUB>2</SUB><SUP>+</SUP> on the former, subsequent to isotope exchange on the H<SUB>2</SUB>O surface. Ultra-low-energy collision-induced dihydrogen ion production is also observed from alkanol surfaces, with decreasing efficiency as the alkyl chain length increases. There is no corresponding reaction on solid hexane. This endothermic reaction, with implications for interstellar chemistry and plasma etching processes, is proposed to occur as a result of stabilization of the other reaction product, a hydroxyl radical (OH•), on water surfaces through hydrogen-bonding interactions with the surface. These results point to an interesting chemistry involving ultra-low-energy ions on molecular solids

Low energy ion scattering investigations of n-butanol-ice system in the temperature range of 110-150 K

We have investigated the interaction of n-butanol (NBA) with thin layers of water ice prepared in ultra high vacuum in the temperature range of 110-150 K. From the mass spectra of the chemically sputtered species, created upon the collision of low energy (&#8805;30 eV) Ar+ ions, we study the process of diffusive mixing of NBA with water ice, at the molecular level. The results show that NBA undergoes diffusive mixing with H2O. Even after depositing 1000 monolayers (MLs) of amorphous solid water (ASW) over NBA, both the species are observed on the surface. However, when NBA is deposited over ASW, no water is seen on the surface above 3-5 MLs of NBA. This could be interpreted as the absence of diffusive mixing in this system or surface segregation of NBA, in view of its lower surface energy just as in the case of liquid alcohols. An isomeric alcohol, namely, tert-butyl alcohol (TBA), also behaves similarly. Although the presence of NBA and TBA is detected, in the presence of ASW, they undergo selective ionization, giving specific peaks in the mass spectrum. D2O behaves in a manner similar to that of H2O. Preliminary experiments with other alcohols; namely, methanol, ethanol, and propanol were also done, and the results suggest that incomplete diffusion or surface segregation begins with propanol