Manipulation of Gaseous Ions with Acoustic Fields at Atmospheric Pressure.

The ability to controllably move gaseous ions is an essential aspect of ion-based spectrometry (e.g., mass spectrometry and ion mobility spectrometry) as well as materials processing. At higher pressures, ion motion is largely governed by diffusion and multiple collisions with neutral gas molecules. Thus, high-pressure ion optics based on electrostatics require large fields, radio frequency drives, complicated geometries, and/or partially transmissive grids that become contaminated. Here, we demonstrate that low-power standing acoustic waves can be used to guide, block, focus, and separate beams of ions akin to electrostatic ion optics. Ions preferentially travel through the static-pressure regions ("nodes") while neutral gas does not appear to be impacted by the acoustic field structure and continues along a straight trajectory. This acoustic ion manipulation (AIM) approach has broad implications for ion manipulation techniques at high pressure, while expanding our fundamental understanding of the behavior of ions in gases.

Application of a Modified 3D-PCSI-MS Ion Source to On-Site, Trace Evidence Processing via Integrated Vacuum Collection.

Trace evidence, including hair, fibers, soil/dust, and gunshot residue (GSR), can be recovered from a crime scene to help identify or associate a suspect with illegal activities via physical, chemical, and biological testing. Vacuum collection is one technique that is employed in recovering such trace evidence but is often done so in a targeted manner, leaving other complementary, chemical-specific information unexamined. Here, we describe a modified 3D-printed cone spray ionization (3D-PCSI) source with integrated vacuum collection for on-site, forensic evidence screening, allowing the processing of targeted physical traces and nontargeted chemical species alike. The reported form factor allows sample collection, onboard extraction, filtration, and spray-based ionization in a singular vessel with minimal handling of evidence by the operator. Utilizing authentic forensic evidence types and portable MS instrumentation, this new method was characterized through systematic studies that replicate CSI applications. Reliability in the form of false positive/negative response rates was determined from a modest, user-blinded data set, and other attributes, such as collection efficacy and detection limit, were examined.

MODERN PLASMA-BASED DESORPTION/IONIZATION: FROM ATOMS AND MOLECULES TO CHEMICAL SYNTHESIS.

Since the first mass spectrometry (MS) experiments were conducted by Thomson and Aston, plasmas have been used as ionization sources. Historically, plasma ion sources were used for these experiments because they were one of the few known sources of gas-phase ions at the time and they were relatively simple to setup and operate. Since then, developments in plasma ionization have continued to inform and motivate advances in other areas of MS. For example, plasma-desorption MS demonstrated ionization of large peptides and polymers more than 10 years before the first descriptions of electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). As a result, significant effort was placed on development of ionization approaches, mass analysis, and detection approaches for very large molecules: even before the advent of ESI and MALDI. Since then, new analytical challenges and opportunities in plasma ionization have arisen. In this review, the emerging trends in plasma-based ionization for several areas of MS will be discussed, including molecular ionization, elemental ionization, hybrid elemental and molecular ion sources, and unique chemical transformations. © 2020 John Wiley & Sons Ltd. Mass Spec Rev.

HYSCORE and DFT Studies of Proton-Coupled Electron Transfer in a Bioinspired Artificial Photosynthetic Reaction Center.

The photosynthetic water-oxidation reaction is catalyzed by the oxygen-evolving complex in photosystem II (PSII) that comprises the Mn4CaO5 cluster, with participation of the redox-active tyrosine residue (YZ) and a hydrogen-bonded network of amino acids and water molecules. It has been proposed that the strong hydrogen bond between YZ and D1-His190 likely renders YZ kinetically and thermodynamically competent leading to highly efficient water oxidation. However, a detailed understanding of the proton-coupled electron transfer (PCET) at YZ remains elusive owing to the transient nature of its intermediate states involving YZ⋅. Herein, we employ a combination of high-resolution two-dimensional 14N hyperfine sublevel correlation spectroscopy and density functional theory methods to investigate a bioinspired artificial photosynthetic reaction center that mimics the PCET process involving the YZ residue of PSII. Our results underscore the importance of proximal water molecules and charge delocalization on the electronic structure of the artificial reaction center.

Calixsmaragdyrin: A Versatile Ligand for Coordination Complexes.

The Ru(II) and BF2 complexes of calixsmaragdyrin were prepared under simple reaction conditions and characterized by HR-MS, 1D and 2D NMR spectroscopy, optical spectroscopy, and electrochemistry, and the structure of the Ru(II) complex of calixsmaragdyrin was elucidated by X-ray crystallography. The crystal structure of the Ru(II) complex revealed that the Ru(II) ion is hexacoordinate with the three pyrrole nitrogen ligands from the tripyrrin unit of the calixsmaragdyrin macrocycle, and the remaining coordination sites of Ru(II) ion were occupied by two carbonyl groups and one hydroxyl (-OH) group. The calixsmaragdyrin macrocycle in the Ru(II) complex was distorted with a dome-like structure. In the BF2 complex of calixsmaragdyrin, the BF2 unit was bound to two pyrrolic nitrogens of the dipyrrin moiety of calixsmaragdyrin as deduced by detailed 1- and 2-dimensional NMR spectroscopy studies. The Ru(II) complex displayed a strong Soret-like absorption band at 449 nm with the absence of Q-bands, whereas the BF2 complex showed a Soret-like band at 475 nm with two well-defined Q-bands at 787 and 883 nm, respectively. Quantum mechanical DFT calculations yielded relaxed equilibrium structures that were similar to the X-ray crystal structures, and the related charge density distributions indicated that the d orbital of the Ru(II) ion was contributing to the HOMO and LUMO states. In addition, TD-DFT calculations successfully reproduced the large bathochromic shifts, oscillator strengths, and electronic transitions that were observed in the experimental absorption spectra of all three complexes. Both the Ru(II) and the BF2 complexes of calixsmaragdyrin were stable under redox conditions.